CN1216073A - Martensitic-Austentitic steel - Google Patents

Martensitic-Austentitic steel Download PDF

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Publication number
CN1216073A
CN1216073A CN 97193736 CN97193736A CN1216073A CN 1216073 A CN1216073 A CN 1216073A CN 97193736 CN97193736 CN 97193736 CN 97193736 A CN97193736 A CN 97193736A CN 1216073 A CN1216073 A CN 1216073A
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Prior art keywords
content
steel
weight
martensite
content range
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CN 97193736
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Chinese (zh)
Inventor
P·埃恩斯特
P·J·乌戈维策尔
M·斯佩德尔
R·思泰恩斯
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ABB Research Ltd Switzerland
ABB Research Ltd Sweden
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ABB Research Ltd Switzerland
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Publication of CN1216073A publication Critical patent/CN1216073A/en
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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
    • 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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Heat Treatment Of Articles (AREA)

Abstract

This invention concerns a martensitic-austentitic steel consisting essentially (in wt%) of: 8 to 15% chromium, 0.5 to 2.5% molybdenum, up to 2% tungsten, 4 to 10% cobalt, 0.5 to 6% nickel, 2.5 to 8% manganese, 0.1 to 1.0% vanadium, 0.05 to 0,25% nitrogen, up to 0.2% carbon, the rest being iron with impurities. This martensitic-austentitic steel can be used, in particular, as material for rotors or rotor disks in gas turbines operating at temperatures above 450 DEG C. The adjustment of the two phase martensitic-austentitic structure is done by heat treatment of the solution annealed and quenched steel structure in a temperature range between 550 DEG C and 650 DEG C.

Description

Martensitic-Austentitic steel
Invention field
The present invention relates to a kind of martensitic-Austentitic steel, the martensite-austenitic steel of the component materials that bears creep stress in the internal combustion turbine.
Background of invention
But the present state in present technique field is to adopt the chromium steel of modifier treatment as the material that is used for thermoelectric power station, especially for the material of rotor or rotor wheel.With compare with nickel-based superalloy, but the characteristics of the chromium steel of modifier treatment are can be through nondestructiving inspecting test preferably.In addition, it also has lower thermal expansivity and high thermal conductivity, has so just strengthened the performance of heat-resistant anti-fatigue.Yet when temperature surpassed 450 ℃, this quenched and tempered steel was in the requirement that just can not satisfy expection aspect heat-resisting, creep resistance and the toughness.
But known a kind of label is the martensitic steel of the modifier treatment of X12CrNiMo12.This steel deironing also comprises outward: the N of V, the 0.02-0.05% of Mo, the 0.2-0.35% of Ni, the 1.3-1.8% of Cr, the 2-2.6% of Mn, the 11-12% of the C of 0.10-0.14%, the Si of 0.10-0.40%, 0.5-0.9% and common impurity.This steel and has the quite high high temperature yield limit and quite high creep-resistant property in being lower than 450 ℃ temperature range.Yet when temperature surpassed 450 ℃, this high temperature yield limit and creep-resistant property were just not enough in addition, and this steel has tangible embrittlement trend under higher temperature.
Summary of the invention
The purpose of this invention is to provide a kind of martensite-austenitic steel that is used for gas turbine rotor or gas turbine rotor impeller, it has enough resistance toheats and toughness by 450 ℃ at least 550 ℃ temperature range.
According to the present invention, can realize this point according to the characteristic in first claim.
Core of the present invention is to adjust the very meticulous two-phase microtexture of being made up of tempered martensite and thermodynamically stable formula body difficult to understand.This steel mainly comprises: the manganese of the chromium of 8-15%, the cobalt of 4-10%, 2.5-8%, the nickel of 0.5-6%, reaches 2% tungsten, the vanadium of 0.1-0.5%, the carbon of 0.05-0.2% at the molybdenum of 0.5-2.5%, the nitrogen of 0.05-0.25%, all the other are iron and the common impurity that forms under melting condition.
Be fully according to foregoing advantage reality of the present invention as can be seen, even the steel that forms according to double structure is in the temperature more than 450 ℃, also have the high high temperature yield limit and high creep-resistant property, and because its high structural stability presents low embrittlement trend.
Form further advantageous embodiment according to each dependent claims.
Inventive embodiment
For using the steel developed, the present invention mainly comprises by weight: the carbon of the molybdenum of the manganese of the chromium of 8-15%, the cobalt of 4-10%, 2.5-8%, the nickel of 0.5-6%, 0.5-2.5%, the vanadium that reaches 2% tungsten, 0.1-1.0%, 0.05-0.2%, the nitrogen of 0.05-0.25% and can be by casting or by the powder metallurgy process manufacturing.
Chromium steel known and the industrial 9-12% that adopts be since on the dislocation grid that in this tempered martensite, forms very meticulous sedimentary stabilization reach its heat-resisting and creep-resistant property.Using for the present invention in the steel of development, except this meticulous throw out, also introducing a kind of face-centered cube phase (formula body difficult to understand),, just helping to improve heat-resisting and creep-resistant property because it low spread voluntarily and formed phase interface.Is known containing austenite in the art as the Ma Shiti steel of second phase of improving creep property.Yet, to compare with steel of the present invention, its difference is that their formula body portion difficult to understand is not thermodynamically stable, makes for thermal fatigue it is very responsive.
Below, the concrete preferred amounts of introducing for every kind of element, and the selected alloy of alloy of the present invention constitutes the reason of scope.
Utilization is dissolved into chromium in this sosoloid to improve antioxidant property.By forming hexagonal chromium nitride, Cr also can help to improve creep-resistant property.In order to realize this point, the minimum content of Cr is required to be 8% (weight).Yet chromium content should not surpass 15% (weight), otherwise can form δ-ferrite, reduces to cause toughness and hot strength.Therefore, be about 8-15% (weight), be preferably 9-12% (weight), particularly 10% (weight) for the suitable scope of chromium.
In steel of the present invention, manganese is effective especially to the solubleness that improves the nitrogen in the formula difficult to understand tagma.For in the solution annealing process dissolving hexagonal stable nitride (Cr, V) 2(content of Mn is minimum to be 2.5% (weight) for V, Cr) N for N and cuboidal stable nitride.In the process of temper, manganese is collected in the formed austenite, and reduces its martensitic starting temperature fatefully, and promptly stablized should Austria's formula body for manganese.Also because of this reason, the content of manganese should be 2.5% (weight) at least.Yet, becoming austenite completely in order to prevent this alloy, Mn content should not surpass 8% (weight).Therefore, the OK range of manganese is about 2.5-8 (weight), is preferably 3.5-6.5% (weight), particularly is about 5% (weight).
Nickel has increased the toughness at martensite chromium steel, because it reduces δ-ferritic content effectively.Similar to manganese, nickel has been stablized the formula body phase difficult to understand in double structure.Owing to this reason, this alloy should comprise the Ni of 0.5% (weight) at least.Nickel content surpasses 6% (weight), Ac 3Name a person for a particular job and reduce greatly.Therefore, be about 0.5-6% weight, be preferably 2-5% (weight), particularly be about 3.7% (weight) by the OK range of nickel.
Cobalt improves the equivalent of nickel to such degree, that is, alloy is solidified with austenite by molten state.Therefore, the micropore formation of having avoided the effusion of nitrogen and having caused thus.Therefore, the content of Co should be 4% (weight) at least.Yet Co content should not surpass 10% (weight), so that this alloy has sufficiently high Ac 3Temperature.Therefore, the OK range of cobalt is about 4-10% (weight), is preferably 5-8% (weight), particularly is about 6% (weight).
Molybdenum can improve tempering characteristics and resistance toheat, and therefore, minimum content should be kept 0.2% (weight).Mo content should be no more than 2.0% (weight), otherwise may produce a large amount of Laves' phases (Lavesphase).Therefore the OK range of molybdenum is 0.5-2.5% (weight), is preferably 1.0-2.0% (weight), particularly about 1.5% (weight).
The effect of dove is similar to molybdenum.Owing to have the danger that forms Laves' phases, so content should not surpass 2% (weight).Therefore the content of tungsten is 0-2% (weight), is preferably to be lower than 1% (weight).
Vanadium forms the fine and close dispersoid of a kind of cohesive and part cohesive cube nitride with nitrogen and small part chromium, and it determines heat-resisting and creep-resistant property basically.Wherein the content of V is at least 0.1% (weight) when forming alloy.Yet because vanadium can increase the trend that delta ferrite forms, so the content of V should not surpass 1% (weight).Preferably the content of vanadium is 0.15-0.65% (weight).
Under the atom dissolved state, nitrogen can promote not had in opposite directions by austenite the austenitic transformation of diffusion in process of cooling.This has just guaranteed modifier treatment.In addition, can with V and Cr, also may form described nitride with Nb, Ti and Ta.Therefore, nitrogen should form alloy with stoichiometric quantity.Because N possibility effusion in solidification process is not so its upper limit should surpass 0.25% (weight).Therefore the content of N is about 0.05-0.25% (weight), is preferably 0.07-0.15% (weight).
Carbon can promote molecular formula Cr with chromium 23C 6The formation of carbide.Take temperature according to its stoichiometric calculation, the chromium that this carbide is removed from matrix is than the Cr that forms in steel of the present invention 2The chromium that N removes is more.Owing to this reason, the content of carbon should be no more than 0.2% (weight), is preferably 0.1% (weight).
Niobium, titanium, zirconium and tantalum all are alloying elements, can form the various specific nitride of MX type with vanadium.Their effect at first is when a small amount of the interpolation, can strengthen V (N, the stability of C) separating out.Yet under high-content, the stability of nitride is high in the solution treatment process and can not be dissolved.Owing to this reason, the total content of these elements is restricted to 0.5%
Boron can increase the anti-alligatoring performance of various precipitates.Because this can cause liquate, so content must be limited in 0.02%.
Often run into because in the impurity that working condition forms, the content that does not for example have plain phosphorus, sulphur, antimony, tin and arsenic should not surpass the amount shown in the table 2 in the back various.This is for being avoided temper embrittlement necessary.
Steel of the present invention has martensite-austenitic structure, and this structure forms by modifier treatment.This hardening and tempering method comprises solution annealing, quenches and tempering subsequently.
Solution annealing should be carried out at 1050 ℃≤T≤1250 ℃ T., is preferably 1100 ℃≤T≤1230 ℃, and particularly 1200 ℃, so that the dissolving molecular formula is all nitride of VN.Through temper, adjust the quenching degree of austenitic content and martensitic phase.For required formula body component difficult to understand is adjusted to 15-45%, annealing temperature will be chosen in 550 ℃≤T≤650 ℃, is preferably 580 ℃≤T≤630 ℃.
Embodiment
Below, with way of example the particularly preferred embodiment of above-mentioned various alloys is described in more detail, be labeled as alloy 817 here.The composition of alloy 817 can be taken from table 1 and table 2.The maximum level of some presumable impurity of expression in the table 2.
After solution annealing and quench treatment, alloy is little in 600 ℃ of following tempering 4.After the thermal treatment, the structure of formation is biphase martensite-austenite, and the content of austenite phase is about 37%, and the phase region size is the 200-300 nanometer.
Characteristic with alloy 817 of the present invention in table 3 compares with the previous alloy X12CrNiMo12 that introduces.
According to table 3, the alloy 817 of comparing with alloy X12CrNiMo12 shows the characteristic of major tuneup.High heat-resisting and creep-resistant property makes that it can be as rotor material and the rotor wheel material at the internal combustion turbine of temperature under up to 550 ℃.
Table 1
Element ????Cr ????Mo ????W ????Co ????Ni ????Mn ??V
% (weight) ????10 ????0.5 ????1.5 ????6.0 ????3.7 ????5.0 ??0.5
Element ????Nb ????Ti ????Ta ????N ????C ????Fe
% (weight) ?≤0.01 ????0.01 ??≤0.01 ????0.12 ??≤0.01 All the other
Table 2
Element ????P ??????S ??????Sb ??????Sn ????As
% (weight) ?≤0.005 ???≤0.002 ????≤0.003 ????≤0.005 ??≤0.005
Table 3
Characteristic ???817 ??X12CrNiMo12
Yield strength R p0.2(RT),〔MPa〕 ???970 ??????800
Yield strength R p0.2(200℃),〔MPa〕 ???920 ??????730
Yield strength R p0.2(300℃),〔MPa〕 ???860 ??????690
Yield strength R p0.2(400℃),〔MPa〕 ???850 ??????650
Yield strength R p0.2(500℃),〔MPa〕 ???800 ??????520
Yield strength R p0.2(600℃),〔MPa〕 ???650 ???????-
Elongation at break (RT), A 5〔％〕 ????20 ???????12
Lack D ballistic work Av (RT) (J) ????80 ?????30-50
FATT 50, (℃); The Av/ higher position, (J) ??-30,80 ???????-
Creep-resistant property, Rm/100000h/500 ℃, (MPa) ??≥300 ??????170

Claims (6)

1. martensite-austenitic steel, its composition is mainly by weight: the manganese of the cobalt of the chromium of 8-15%, the molybdenum of 0.5-2.5%, the tungsten up to 2%, 4-10%, the nickel of 0.5-6%, 2.5-8%, the vanadium of 0.1-1.0%, the nitrogen of 0.05-0.25%, the carbon up to 0.2%, all the other compositions are iron and various impurity.
2. martensite-the austenitic steel described in claim 1, it is characterized in that, the content range of chromium be the content range of 9-12% and/or molybdenum be the content range of 1.0-2.0% and/or cobalt be the content range of 5-8% and/or nickel be the content range of 2-5% and/or manganese be the content of 3.5-6.5% and/or tungsten be 1.0% and/or the content range of vanadium be that the content range of 0.15-0.65% and/or nitrogen is that the content of 0.07-0.15% and/or carbon is up to 0.1%.
3. as the martensite-austenitic steel of claim 1 or 2, it is characterized in that, contain maximum total amount and be 0.5% niobium, titanium, zirconium and tantalum.
4. as claim 1, martensite-austenitic steel of 2 or 3, it is characterized in that the content of boron is 0.02% to the maximum.
As described martensite-austenitic steel one of among the claim 1-4 as the heat-resisting and application of creep resistance material in thermoelectric power station.
6. as the heat treating method of described martensite-austenitic steel one of among the claim 1-4, it is characterized in that, this method is included in 550 ℃-650 ℃ the temperature range carries out tempering to the steel alloy that is under solution annealing and the as-quenched condition, forms a kind of austenitic structure that volume share is 20%-50% that contains thus.
CN 97193736 1996-04-12 1997-03-25 Martensitic-Austentitic steel Pending CN1216073A (en)

Applications Claiming Priority (2)

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DE1996114407 DE19614407A1 (en) 1996-04-12 1996-04-12 Martensitic-austenitic steel
DE19614407.8 1996-04-12

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CN (1) CN1216073A (en)
CA (1) CA2251805A1 (en)
DE (1) DE19614407A1 (en)
NO (1) NO984756L (en)
PL (1) PL329050A1 (en)
WO (1) WO1997039158A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103526131A (en) * 2013-10-31 2014-01-22 万宝力不锈钢制品（东莞）有限公司 High-strength stainless steel coffee pot material and preparation method thereof

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BR0006678A (en) * 1999-07-12 2001-05-02 Mmfx Steel Corp Of America Process for manufacturing a tough, corrosion resistant and high mechanical resistance alloyed carbon steel, and, product
DE10063117A1 (en) * 2000-12-18 2003-06-18 Alstom Switzerland Ltd Conversion controlled nitride precipitation hardening tempering steel
CN1333098C (en) * 2005-06-24 2007-08-22 寇生瑞 Iron base rare earth high chromium steel impellor blade
CN102154592B (en) * 2011-03-04 2012-11-21 燕山大学 Micro-alloying martensite stainless steel for blades of water turbine and manufacturing method thereof
CN102242313B (en) * 2011-07-18 2012-12-26 山东建筑大学 High-hardness silver-bearing martensite antibacterial stainless steel

Family Cites Families (7)

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DE959681C (en) * 1943-08-14 1957-03-07 Eisen & Stahlind Ag Blades and similarly stressed components of gas turbines and other similarly or similarly stressed objects
DE1082739B (en) * 1953-05-29 1960-06-02 Nyby Bruk Ab Use of non-precipitation-hardening, overheating-insensitive alloys
JPS63171856A (en) * 1987-01-09 1988-07-15 Hitachi Ltd Heat-resisting steel and gas turbine using same
JPH04154921A (en) * 1990-10-16 1992-05-27 Nisshin Steel Co Ltd Manufacture of high strength stainless steel strip having excellent shape
DE69516336T2 (en) * 1994-01-26 2000-08-24 Kawasaki Steel Corp., Kobe METHOD FOR PRODUCING A STEEL SHEET WITH HIGH CORROSION RESISTANCE
JPH07216451A (en) * 1994-01-31 1995-08-15 Nisshin Steel Co Ltd Production of stainless steel material having high welding softening resistance, high strength, and high ductility
JPH07268561A (en) * 1994-03-29 1995-10-17 Nisshin Steel Co Ltd High strength stainless steel excellent in hot workability and free from welding softening

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103526131A (en) * 2013-10-31 2014-01-22 万宝力不锈钢制品（东莞）有限公司 High-strength stainless steel coffee pot material and preparation method thereof
CN103526131B (en) * 2013-10-31 2015-07-22 万宝力不锈钢制品（东莞）有限公司 High-strength stainless steel coffee pot material and preparation method thereof

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NO984756D0 (en) 1998-10-12
DE19614407A1 (en) 1997-10-16
CA2251805A1 (en) 1997-10-23
NO984756L (en) 1998-10-12
PL329050A1 (en) 1999-03-01
WO1997039158A1 (en) 1997-10-23
JP2000510904A (en) 2000-08-22
EP0907758A1 (en) 1999-04-14

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