CN102031461A - Heat-resisting alloy with high yield ratio, high toughness and long-run elasticity stability - Google Patents

Heat-resisting alloy with high yield ratio, high toughness and long-run elasticity stability Download PDF

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CN102031461A
CN102031461A CN 201010516992 CN201010516992A CN102031461A CN 102031461 A CN102031461 A CN 102031461A CN 201010516992 CN201010516992 CN 201010516992 CN 201010516992 A CN201010516992 A CN 201010516992A CN 102031461 A CN102031461 A CN 102031461A
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张十庆
李方
王宏
聂尊誉
邹兴政
唐锐
赵光明
刘庆宾
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CHONGQING METER MATERIALS INST
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Abstract

The invention discloses a heat-resisting alloy with high yield ratio, high toughness and long-run elasticity stability, which is characterized by comprising the following components in percentage by weight: less than or equal to 0.06 percent of C, less than or equal to 0.6 percent of Si, 0.8 to1.2 percent of Mn, 26.5 to 29.5 percent of Ni, 15.0 to 18.0 percent of Cr, 1.0 to 1.5 percent of Mo, 2.80 to 3.30 percent of Ti, less than or equal to 0.6 percent of Al, 0.003 to 0.006 percent of B, 0.005 to 0.05 percent of Ca, 0.005 to 0.05 percent of Mg, and the balance of Fe. In the new alloy, alloy elements are added on the basis of Fe-Cr-Ni, the high yield ratio and high toughness are achieved, and the long-run elasticity stability is kept; and by controlling a Ti/Al ratio, optimizing the microstructures of intermetallic compounds and regulating the contents of B, Mo and C, the grain boundary strengthening effect is improved. The new ally fills up a blank on the research of the alloy in China, and meets the property requirements on high yield ratio, high toughness and long-run elasticity stability of the conventional aero high-temperature alloy parts of China.

Description

A kind of high-yield-ratio high tenacity long-run elasticity stability refractory alloy
Technical field
The present invention relates to a kind of alloy, particularly a kind of high-yield-ratio high tenacity long-run elasticity stability refractory alloy.
Background technology
Heat-resisting elastic alloy is a kind of of superalloy, and it is meant at high temperature can keep sufficient intensity and the good oxidation-resistance and the alloy of elastic performance.Heat-resisting elastic alloy for industrial sector of working and utilisation technology, has significant meaning under hot conditions.
Initial development work starts from the '30s, and it is owing to needing more heat-stable elastic element material to grow up in aircraft manufacturing.At the forties initial stage,, the use temperature of superalloy in aircraft raise, thereby make heat-resisting elastic alloy along with needs are developed owing to press for the technology of advanced gas turbine engines.
The research of heat-resisting elastic alloy material is widely used at many industrial circles, and its typically used is as follows: 1, automation instrument, valve spring; 2 large aircrafts, engine throttle spring piece; 3 differential pressure diaphragms and corrugated tube etc.; 4 migel relay spring pieces; Support spring sheet in 5 television picture tubes; 6 gasoline Wankel engine are scraped leaf spring or the like.It is operated under 500 ℃~550 ℃ the temperature, 610 ℃ of top temperatures.Performances such as, fatigue lifetime lax to its high temperature oxidation resistance, resistant to high-temperature stress have strict requirement, to guarantee that under certain working pressure and temperature spring can accurately be opened, closure valve, satisfy the requirement of equipment works better.
Except that aircraft, boats and ships, industry and vehicle with the gas turbine, heat-resisting elastic alloy also is used for outer space vehicle, rocket engine, experimental aircraft, nuclear reactor, submarine, steam power plant device, petrochemical equipment and other high-temperature uses now.
Alloys such as A286, W545, V57 have been invented by the U.S. in last century, but such alloy yield tensile ratio is not high, and this alloy will cause elastic failure 550 ℃ of uses simultaneously.Early stage Soviet Union expert has also developed and has been applied on the opportunity of combat
Figure BSA00000315397400021
Deng alloy, this material succeed in developing the great performance that improves this state's aircraft, but the toughness of this material is not best.China has also developed similar alloy material for example GH2132,3YC27 etc., and this type of material is at last under the situation that has satisfied high-yield-ratio, A≤4% even A≤2% that has, and this machine-shaping to elastic element causes great difficulty.
Common Fe-Cr-Ni is that heat-resisting elastic alloy has high intensity, possesses high toughness and at high temperature keeps long-run elasticity stability person few but be both.China has become the aviation big country after the U.S., Russia at present, and the demand of this type of heat-resisting elastic alloy is become the trend of rising year by year.China 2009 high temperature alloy as 973 major projects, visible China at present is to the widespread demand of material like that.If an airplane since the element that its heat-resisting elastic alloy is made intensity, toughness, and elasticity on inefficacy has taken place, all will cause the fault of aircraft machine.
Summary of the invention
The object of the present invention is to provide a kind of blank of China on such material of filling up, fill up the deficiency of external analogous material, reduce the high-yield-ratio high tenacity long-run elasticity stability refractory alloy of the cost of alloy material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of high-yield-ratio high tenacity long-run elasticity stability refractory alloy, it is characterized in that being made of following components in weight percentage: C≤0.06, Si≤0.6, Mn:0.8~1.2, Ni:26.5~29.5, Cr:15.0~18.0, Mo:1.0~1.5, Ti:2.80~3.30, Al≤0.6, B:0.003~0.006, Ca:0.005~0.05, Mg:0.005~0.05, surplus are Fe.
The invention belongs to novel material and superalloy technical field, the heat-resisting elastic alloy of the present invention has brand-new chemical ingredients, its high temperature use temperature reaches 610 ℃, require the elastic element of alloy processing not only to possess high strength and high toughness, and require to possess secular resilience stability in use more than 600 ℃.During room temperature: E 〉=200GPa, in the time of 610 ℃, E 〉=160GPa.Room temperature: Rm 〉=1350MPa, Rp0.2 〉=1250MPa, A 〉=9%, Z 〉=40%.Using the back to require still to keep good elastic performance through 5000 hours.
In order to achieve the above object, technical scheme of the present invention improves for the technology that the composition to new alloy carries out brand-new design and processing and preparing technology.The design mix of this alloy becomes to be respectively in table 1 with domestic and international comparative alloy.
Table 1 alloying constituent of the present invention and domestic and international comparative alloy composition
Figure BSA00000315397400031
The heat-proof ability that heat-resisting elastic alloy should have good elasticity also to need simultaneously.Thermostability is the salient features requirement of heat-resistant elastic material, and it is a leading indicator of weighing material resistance to chemical attack in high-temperature medium, particularly resistance of oxidation.Ni is the austenitic main forming element of heat-resisting elastic alloy, and the iron-based high temp high elastic modulus alloy is matrix with the austenite, and austenitic matrix has higher thermo-elasticity than ferrite.From in essence, this is because austenite has face-centered cubic lattice, the atomic arrangement densification, and interatomic bond force rate ferrite is big, and therefore the spread coefficient of iron and other atom is little in the austenite dot matrix, recrystallization temperature height (at least more than 800 ℃).Stable in addition austenite structure improves the toughness of metal, when Ni and Cr coexistence, can improve the solidity to corrosion of alloy greatly; Ni also can suppress the formation of σ, μ, Laves phase, so both can prevent brittle generation, can improve the stability of metal again, thereby improves the use temperature of alloy.Elements such as well-known Cr, Mo, Si, Al, Ti are ferrite formers; Ni, Mn, C etc. are austenite formers.Finally organizing of high temperature steel then by they common decisions.At first to calculate this Cr, Ni equivalent.
Cr Equivalent=Cr%+Mo%+1.55Si%+4Ti%+3.5Al%
Ni Equivalent=Ni%+30C%+0.5Mn%
The stain position is the position of alloy of the present invention in your organization chart of Schaefer in the accompanying drawing 1.
The matrix of alloy of the present invention is Fe-Cr-Ni, adds alloy element on this matrix.
The main strengthening phase element of alloy of the present invention is: C, Ti, Al.
Alloy of the present invention mainly is to make the heat-resisting elastic element with high-yield-ratio, high tenacity, long-run elasticity stability, comprises various whiskers, plane spring, flexible sheet.
Alloy strengthening mode of the present invention mainly is that trace is carbide reinforced, and ageing strengthening combines.
The trace element that alloy of the present invention adds is Ca, Mg etc., strengthens the metallurgical performance and the hot workability of alloy.
Alloy of the present invention is at 610 ℃ of energy life-time service, and reaches respectively more than 99.6% and 99.3% through the resilience stability after 1 hour and 100 hours.
The effect of element is as follows in the alloy of the present invention:
The influence of C
Grain boundary carbide is absolutely necessary in the superalloy, and it plays a part important and favourable to creep rupture strength.The form of carbide can influence the performance of alloy, especially plasticity; And carbide also can influence the chemical stability of matrix by the effect of reactive element.Main carbide type in the nickel-base alloy also is MC, M 6C, M 23C 6And M 7C 3Deng.
The influence of Cr
Chromium is to improve the thermostability element in the nickel base superalloy, adds Cr and can form Cr 2O 3Layer, it has low cationvacancy, can stop metallic element to external diffusion and O, N, S and other harmful element to internal diffusion, can prevent the oxidation and the thermal etching of alloy.
The influence of Ni, Ti, Al
Nickel is strong formation and stable austenite and enlarge the element of austenitic area, improves the thermodynamic stability of steel simultaneously, along with the increase of nickel content can reduce even eliminate ferrite, and significantly reduces the tendency that σ forms mutually.Ni, Ti are the main forming elements of γ ' phase.Distribute by γ ' disperse in matrix, hinder dislocation motion, with reinforced alloys.The high-temperature behavior of nickel-base alloy depends primarily on Al, Ti add-on, and increase Al, Ti total amount can improve the solid solubility temperature and γ ' volume fraction mutually of γ ' phase significantly.
The influence of B, Ca, Mg
Add an amount of B, Ca, Mg and can significantly improve creep rupture life of alloy, reduce creep speed, and significantly improve persistent notch sensitivity, improve the plasticity and the processing characteristics of alloy.The calcium that adds, the amount of magnesium can significantly reduce the quantity of grain boundary carbide, boride and sulfide at 0.005~0.05% o'clock, improved the intergranular bonding force.
The manufacturing process of this alloy
Alloy adopts vacuum induction melting, obtains alloy pig through esr duplex technology again.The alloy hot processing temperature is 1160 ℃~850 ℃.Alloy must carry out solution treatment to eliminate cold working hardening in good time in the cold working process, the solution treatment system is 1080 ℃ of holding temperatures, soaking time 30~60 minutes, shrend.
The alloy user mode is generally aging state, but also solid solution attitude is used.The solution treatment system is 1080 ℃ of holding temperatures, soaking time 30~60 minutes, water-cooled.The timeliness thermal treatment temp is 650 ℃.
The mechanical property of invention alloy sees Table 2.
The mechanical property of table 2 invention alloy
Figure BSA00000315397400051
Invention alloy elastic performance sees Table 3.
Table 3 invention alloy elastic performance
Figure BSA00000315397400061
Press GB/T239-1999 metal wire twisting test method, carrying out twisting test after to the thermal treatment of high-yield-ratio high tenacity long-run elasticity stability heat-resistant alloy wire material timeliness on the torsion testing machine.External similar and golden is Zheng Yiquan with the technical requirements of spring wire material, an anti-circle, and each changes 3 circles, after the test of satisfying service requirements, has proceeded destructive twisting test.The invention alloy wire can reach reversing of continuous 5 circles, just through 1800 ° reverse.Twisting test the results are shown in Table 4
Table 4 torsion test result
Figure BSA00000315397400062
Press GB/T238-2002 metal wire bend test method, to the laggard line bend test of high-yield-ratio high tenacity long-run elasticity stability heat-resistant alloy wire material timeliness thermal treatment of two kinds of specifications of two heat (batch) numbers (Φ 3.2, Φ 1.0).External with such spring alloy silk material technical requirements be crooked 6 times and surface cracking do not occur, fold, phenomenon such as burr.Pliability test the results are shown in Table 5.
Table 5 pliability test result
Figure BSA00000315397400071
The beneficial effect of a kind of high-yield-ratio high tenacity of the present invention long-run elasticity stability refractory alloy is, new alloy is on the basis of Fe-Cr-Ni, add alloying element, satisfying under tough implementations high-yield-ratio and high, and keep long-run elasticity stability,, optimize the tissue of intermetallic compound by the ratio of control Ti, Al, adjust the composition of B, Mo, C, improve the grain-boundary strengthening effect.The blank of China on this alloy research filled up in the success of this new alloy.Satisfy the performance requriements of the at present a lot of aerial high-temperature alloy component needs high-yield-ratios of China, high tenacity, long-run elasticity stability.
Description of drawings
Fig. 1 is the positional structure synoptic diagram of new invention alloy of the present invention in the Schaefler organization chart;
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing, but therefore do not limit the present invention among the described scope of embodiments.
Embodiment 1
A kind of high-yield-ratio high tenacity long-run elasticity stability refractory alloy, it is characterized in that being made of following components in weight percentage: C 0.034, Si 0.4, Mn 1.04, Ni 27.5, Cr 16, Mo 1.4, Ti 3.05, Al 0.51 B 0.0033, Ca0.01, Mg0.01, surplus is Fe.The alloy pig of producing through hot-work, be cold worked into a material, band, bar, tubing, is applied to the required all kinds of high-intensity high-tenacities of industries such as aviation, petrochemical industry, metallurgy, electromechanics, the high temperature resistant elastic element of long-run elasticity stability.
Embodiment 2
A kind of high-yield-ratio high tenacity long-run elasticity stability refractory alloy, it is characterized in that being made of following components in weight percentage: C 0.024, Si 0.35, Mn 1.10, Ni 28, Cr 16.5, Mo 1.3, Ti 2.8, Al 0.4B 0.0033, Ca0.005, Mg0.005, surplus is Fe.By the vacuum melting alloy pig that obtains of esr duplex technology manufacturing again, through hot-work, be cold worked into bar, forging, be applied to high strength heat resistant rotor, the heat-resisting forging in power station.
Embodiment 3
A kind of high-yield-ratio high tenacity long-run elasticity stability refractory alloy, it is characterized in that being made of following components in weight percentage: C 0.040, Si 0.35, Mn 1.10, Ni 28, Cr 16.5, Mo 1.3, Ti 2.8, Al 0.4 B 0.0033, Ca0.05, Mg0.05, surplus is Fe.Alloy adopts vacuum induction melting, obtains alloy pig through esr duplex technology again.The alloy hot processing temperature is 1160 ℃~850 ℃.Through hot-work, be cold worked into bar, forging, be applied to high strength heat resistant rotor, the heat-resisting forging in power station.Alloy must carry out solution treatment to eliminate cold working hardening in good time in the cold working process, the solution treatment system is 1080 ℃ of holding temperatures, soaking time 30~60 minutes, shrend.
Described embodiments of the present invention though combine, those of ordinary skill in the art can make various distortion or modification within the scope of the appended claims.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.

Claims (1)

1. high-yield-ratio high tenacity long-run elasticity stability refractory alloy, it is characterized in that being made of following components in weight percentage: C≤0.06, Si≤0.6, Mn:0.8~1.2, Ni:26.5~29.5, Cr:15.0~18.0, Mo:1.0~1.5, Ti:2.80~3.30, Al≤0.6, B:0.003~0.006, Ca:0.005~0.05, Mg:0.005~0.05, surplus are Fe.
CN 201010516992 2010-10-22 2010-10-22 Heat-resisting alloy with high yield ratio, high toughness and long-run elasticity stability Pending CN102031461A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268611A (en) * 2011-07-07 2011-12-07 徐振伟 Fe-based heat-resisting alloy and preparation method thereof
CN105483492A (en) * 2015-12-08 2016-04-13 江苏华冶科技有限公司 High-temperature-resisting alloy material for radiant tube and casting process of high-temperature-resisting alloy material
CN108823382A (en) * 2018-08-02 2018-11-16 安徽恒利增材制造科技有限公司 A kind of iron-base superalloy accumulation heat treatment process and its performance study
CN113061802A (en) * 2021-02-07 2021-07-02 中国科学院金属研究所 High-strength austenitic aged stainless steel resistant to corrosion of concentrated nitric acid containing oxidative ions and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015826A (en) * 2003-06-24 2005-01-20 Nippon Seisen Co Ltd Stainless steel wire for heat resistant spring, and heat resistant spring product obtained by using the same
CN1701126A (en) * 2003-08-07 2005-11-23 住友金属工业株式会社 Duplex stainless steel and manufacturing method thereof
CN101642782A (en) * 2009-07-15 2010-02-10 钢铁研究总院 Method for preparing Cr-Ni system Austenitic heat-resistant steel springs and cool-drawn steel wires thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015826A (en) * 2003-06-24 2005-01-20 Nippon Seisen Co Ltd Stainless steel wire for heat resistant spring, and heat resistant spring product obtained by using the same
CN1701126A (en) * 2003-08-07 2005-11-23 住友金属工业株式会社 Duplex stainless steel and manufacturing method thereof
CN101642782A (en) * 2009-07-15 2010-02-10 钢铁研究总院 Method for preparing Cr-Ni system Austenitic heat-resistant steel springs and cool-drawn steel wires thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268611A (en) * 2011-07-07 2011-12-07 徐振伟 Fe-based heat-resisting alloy and preparation method thereof
CN102268611B (en) * 2011-07-07 2012-12-19 徐振伟 Fe-based heat-resisting alloy and preparation method thereof
CN105483492A (en) * 2015-12-08 2016-04-13 江苏华冶科技有限公司 High-temperature-resisting alloy material for radiant tube and casting process of high-temperature-resisting alloy material
CN108823382A (en) * 2018-08-02 2018-11-16 安徽恒利增材制造科技有限公司 A kind of iron-base superalloy accumulation heat treatment process and its performance study
CN113061802A (en) * 2021-02-07 2021-07-02 中国科学院金属研究所 High-strength austenitic aged stainless steel resistant to corrosion of concentrated nitric acid containing oxidative ions and preparation method thereof
CN113061802B (en) * 2021-02-07 2022-05-31 中国科学院金属研究所 High-strength austenitic aged stainless steel resistant to corrosion of concentrated nitric acid containing oxidative ions and preparation method thereof

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Application publication date: 20110427