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CN105838925A - Nickel-based alloy resistant to high temperature oxidation - Google Patents

Nickel-based alloy resistant to high temperature oxidation Download PDF

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Publication number
CN105838925A
CN105838925A CN201510012838.7A CN201510012838A CN105838925A CN 105838925 A CN105838925 A CN 105838925A CN 201510012838 A CN201510012838 A CN 201510012838A CN 105838925 A CN105838925 A CN 105838925A
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alloy
high temperature
nickel
temperature
temperature oxidation
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CN105838925B (en
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徐文亮
马天军
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Baowu Special Metallurgy Co Ltd
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Baosteel Special Steel Co Ltd
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Abstract

The invention discloses a nickel-based alloy resistant to high temperature oxidation. The alloy comprises components, by weight percentage, no more than 0.1% of C, 15-30% of Cr, 1.0-2.5% of Al, 0.01-1.0% of Ti, no more than 0.3% of Si, no more than 0.5% of Mn, 0.01-0.05% of Mg, 0.002-0.03% of B, 0.01-0.15% of Zr, 0.01-0.02% of N, no more than 0.010% of P, and no more than 0.010% of S, wherein P+S is no more than 0.015%, with the balance being Ni and inevitable impurities. The alloy can resist high temperature oxidation, and has excellent high-temperature-resistant lasting creep resistance. The alloy can be produced through adoption of an electric-arc furnace and refining and can meet requirements of industrial production to a high-temperature-resistant alloy material in large equipment.

Description

High temperature oxidation resisting nickel-base alloy
Technical field
The present invention relates to a kind of nickel-base alloy, more particularly, it relates to high temperature oxidation resisting nickel-base alloy.
Background technology
In nickel-base alloy, high temperature resistant, corrosion-resistant and simultaneously high-temp corrosion-resisting alloy as Ni-based conjunction Three big main application fields of gold generally use different composition Design Mechanism, thus result in its manufacturer Method is the most otherwise varied.For the nickel-base alloy of main high-temperature resistant medium, it is adaptable to petrochemical industry, In the equipments such as metallurgy, high temperature furnace parts and the combustor of temperature 1200 DEG C generally individually use precipitation strength Type high temperature alloy, in alloy, Cr, Al, Ti, Nb, W etc. containing different content form the strengthenings such as γ To improve the element of high-temperature and durable creeping performance.But the subject matter of this kind of alloy has high temperature oxidation stability Can be poor, temperature is low is less than 1100 DEG C in use, causes reduce service life, meanwhile, such alloy by Need in the fabrication process to use vacuum drying oven to smelt in the general intensified element containing high level, be characterized in Batch is little, and lumber recovery is low.The another kind of typical nickel-base alloy being applied to high-temperature medium holds strengthening nickel for solid Base alloy, typical species includes Incoloy 800H etc., and its composition characteristic is a certain amount of for containing only The resistance to oxidation elements such as Al, Ti, Cr, but its content relatively low Al+Ti 1.2wt% (percentage by weight), Therefore it uses temperature general all below 800 DEG C.It addition, in the industrial production, there is a lot of equipment Long-term operation in 1200 DEG C of temperatures above, such as industry annealing furnace, its military service feature is to use temperature Height, production lot are big, longevity of service, replacing parts are difficult, the therefore high-temperature oxydation to material Performance, high-temperature and durable creeping etc. propose the highest requirement, and meanwhile, such piece volumes causes more greatly The size of the material such as steel plate needed is relatively big, therefore smelting ingot shape etc. also certainly will be proposed higher wanting Ask, as used nickel-base alloy as above also to will result in difficulty in actual production.
In addition to conventional high temperature resistant nickel base alloy kind described above, prior art exists 5 kinds and is similar to Use temperature high temperature resistant nickel base alloy (without containing cobalt and Powder Nickel-base) more than 1200 DEG C, Its composition designs as shown in Figure 1.
It will be seen from figure 1 that the universal thinking of such design of alloy is to be added with certain content Rare earth element, for improving the high-temperature behavior of material, meanwhile, in alloy design, another main aspect is Being added with the Al (or Ti) of high level, Al+Ti, at more than wt4%, adds a certain amount of simultaneously Cr puies forward heavy alloyed oxidation resistance.
In sum, existing high temperature resistant environment nickel-base alloy generally use temperature all 1100 DEG C with Under, use temperature high temperature alloy more than 1200 DEG C to typically contain the alloying element of high level, Cannot produce under the electric arc furnace refine smelting condition of Special Steel Enterprise batch production, meanwhile, industrial equipment Development makes a lot of parts need higher service temperature, it addition, the trend that industrial equipment maximizes is the most right The size of exotic material it is also proposed higher requirement, for the alloy containing high-load intensified element Smelt and bring bigger difficulty.
Summary of the invention
The resistance to elevated temperatures that there is material for Chlorimet conventional present in prior art reaches The problems such as Chlorimet performance less than using temperature conditions and conventional is the best, the present invention's Purpose is to provide high temperature oxidation resisting nickel-base alloy.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of high temperature oxidation resisting nickel-base alloy, the percentage by weight of its each composition is: C :≤0.1%, Cr:15~30%, Al:1.0~2.5%, Ti:0.01~1.0%, Si :≤0.3%, Mn :≤ 0.5%, Mg:0.01~0.05%, B:0.002~0.03%, Zr:0.01~0.15%, N: 0.01~0.02%, P≤0.010%, S≤0.010%, wherein, P+S≤0.015%, remaining is Ni and inevitable impurity composition.
According to one embodiment of the invention, the concrete percentage by weight of its each composition is: C:0.02%, Si:0.1%, Mn:0.2%, Cr:15%, Al:1.0%, Ti:1.0%, B:0.03%, Zr:0.10%, P:0.01%, S:0.002%, N:0.01%, Mg:0.05%, remaining is Ni and inevitable impurity composition.
According to one embodiment of the invention, the concrete percentage by weight of its each composition is: C:0.1%, Si:0.2%, Mn:0.2%, Cr:20%, Al:2.0%, Ti:0.3%, B:0.02%, Zr:0.10%, P:0.008%, S:0.01%, N:0.015%, Mg:0.03%, remaining is Ni and inevitable impurity composition.
According to one embodiment of the invention, the concrete percentage by weight of its each composition is: C:0.05%, Si:0.3%, Mn:0.5%, Cr:25%, Al:2.5%, Ti:0.2%, B:0.003%, Zr:0.03%, P:0.008%, S:0.005%, N:0.02%, Mg:0.01%, remaining is Ni and inevitable impurity composition.
According to one embodiment of the invention, the concrete percentage by weight of its each composition is: C:0.02%, Si:0.3%, Mn:0.4%, Cr:22%, Al:2.3%, Ti:0.2%, B:0.002%, Zr:0.02%, P:0.005%, S:0.002%, N:0.018%, Mg:0.02%, remaining Form for Ni and inevitable impurity.
In technique scheme, the high temperature oxidation resisting nickel-base alloy of the present invention is capable of withstanding high-temperature oxydation, Having the nickel base superalloy of good high temperature resistant durable creeping performance, the alloy of the present invention can be adopted simultaneously Produced by the mode of electric arc furnace+refine, to meet commercial production to conjunction high temperature resistant in Large-Scale Equipment The requirement of gold copper-base alloy.
Accompanying drawing explanation
Fig. 1 is the component list of multiple high temperature oxidation resisting nickel-base alloy in prior art;
Fig. 2 is multiple embodiments and the chemical composition contrast table of comparative alloy of the present invention;
Fig. 3 is multiple embodiments and the high temperature tensile properties comparison sheet of comparative alloy of the present invention;
Fig. 4 is multiple embodiments and the antioxygenic property contrast table of comparative alloy of the present invention;
Fig. 5 is multiple embodiments and the high temperature endurance performance comparison sheet of comparative alloy of the present invention.
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with the accompanying drawings with embodiment.
The present invention relates to a kind of high temperature oxidation resisting, there is good high temperature resistant durable creeping performance simultaneously The chemical composition of nickel base superalloy, by weight percentage, its chemical composition proportioning is:
C :≤0.1%, Cr:15~30%, Al:1.0~2.5%, Ti:0.01~1.0%, Si: ≤ 0.3%, Mn :≤0.5%, Mg:0.01~0.05%, B:0.002~0.03%, Zr:0.01~ 0.15%, N:0.01~0.02%, P≤0.010%, S≤0.010%.Wherein, P+S≤0.015%, Remaining is Ni and inevitable impurity composition.Remaining is Ni and inevitable impurity composition.
Each of nickel base superalloy of the present invention addressed below becomes component selections.
The matrix of alloy of the present invention be Ni, Ni be austenitizing formed basic element, it is at oxidation environment In highly stable, add the Cr element of certain content, on the one hand Cr is in Ni-Cr austenite solid solution Oxidation resistance and the resistance to combustion gas corrosion ability of material can be greatly improved, secondly, it is contemplated that invention alloy In user's long term high temperature environment, the high temperature passivating film of Cr formation is highly stable improves the anti-of alloy surface Oxidability, but Cr content is unsuitable too high, too high will affect drawing abillity, by alloy Rollings etc. produce and cause difficulty, therefore control the content of Cr in 15%~30wt% (weight percent Than) between.But when using temperature more than 1200 DEG C, particularly during long-term cold cycling, by right The chromium oxide structure that alloy surface is formed damages, thus the oxidation that accelerated material is under the high temperature conditions, Material failure may can complete at short notice, with the addition of certain content Al element the most in the alloy, Add Al can under the high temperature conditions alloy surface formed one layer of fine and close Al oxide, this layer of oxygen Compound can stop oxygen to matrix internal diffusion, thus improves the stability of Cr and Al oxide structure, Put forward heavy alloyed oxidation resistance further.But the addition of Al element can not be the highest, on the one hand, by In Al improve to 2.5wt% time, the plasticity of material will drastically reduce, will affect material in production process In crystallized ability, on the other hand, Al improves and will bring difficulty to when smelting particularly refine, should For in arc furnace smelting procedure, the control ability of N is limited, and the affinity of Al and N is relatively strong, in smelting The nitride inclusion that refining process is unavoidably formed affects the degree of purity of alloy, and follow-up use is existed shadow Ring, therefore the content of Al is controlled in the range of 1.0~2.5wt%.
C in alloy is prone to the element formation carbides such as Cr, Al affects the non-oxidizability of material, therefore Control at below 0.1wt%.Add appropriate Ti and can improve the solid appearance strengthening effect of material, improve and close The intensity of gold, certainly will improve material intensity under the high temperature conditions, and meanwhile, Ti is stabilizing element, Add appropriate Ti and can improve the Weld Performance after welding by suitable heat treatment.But the addition of Ti Too high, affect oxidation resistance and the weldability of material, therefore control its content 0.01~1.0wt% Between.Alloy adds a certain amount of Si, it is possible to formation resistance to high temperature oxidation layer similar with Al, but its effect Al to be much smaller than, but Si interpolation excess will make materials hot working and oxidation resistance drastically decline, simultaneously It is also possible to form high temperature precipitated phase in the alloy and affects the combination property of material, in the present invention, only make For trace element control.
The interpolation of Mg, Zr, B can put forward heavy alloyed elevated temperature strength, and this dvielement typically exists in the alloy Crystal boundary and interdendritic are assembled, the appropriate elevated temperature strength coordinating interpolation to be remarkably improved material, meanwhile, The interpolation of this dvielement can improve the inclusion morphology in alloy, improves material entirety high temperature oxidation resisting energy Also can improve the stability of superficial oxidation layer while power, improve material oxygen under dynamic oxidation environment Change ability, but this dvielement will result in material plasticity and toughness rapid decrease as added excess, affects material Processing characteristics, therefore in the present invention, its interpolation principle is: Mg:0.01~0.05%;B:0.002~ 0.03%;Zr:0.01~0.15%.
Due to the mode melting of alloy material electric arc furnace+refine of the present invention, although the intensity of material is carried by N Height has superiority but considers to contain in alloy Al, Ti of high level, is easily formed brittle inclusion, therefore controls Make its content between 0.01~0.02%.Meanwhile, the thermoplasticity of high temperature alloy is impacted by P, S, Therefore control its content and be respectively less than 0.01wt%.
The nickel base superalloy of the present invention can use the mode of electric arc furnace+AOD refine to produce, then warp Become ingot after electroslag remelting, be thermally processed into sheet material, forging etc. by modes such as forging, rollings.
Feature of the present invention:
1. by adding the element raising alloy substrates such as appropriate Al, Cr and at high temperature life-time service bar Oxidation resistance under part, can meet temperature requirement of life-time service at 1200 DEG C.
2. the element such as Mg, B, Zr adding trace improves elevated temperature strength and the high-temperature and durable creeping of material Performance, is greatly improved the material recycling performance in Long-term Service under High Temperature condition.
3. being designed by suitable composition, alloy of the present invention can use the mode smelting of Recent Development for Large Scale Electric Arc+refine Refining, is improving lumber recovery, is saving while production cost the also supply of material to large-sized nickel base alloy material Ability has positive practical significance.
Below by the nickel base superalloy selecting concrete composition to form the present invention, and through contrast Test illustrates the feature of nickel base superalloy of the present invention.
Fig. 2 show multiple embodiments of the present invention and the chemical composition contrast table of comparative alloy, wherein A1~A4 is the present invention, for ease of comparing the effect of the present invention, chooses the resistance to of two kinds of conventional component system High-temperature nickel-base alloy B1, B2 carry out reference as a comparison case.In fig. 2, Ni is surplus, examination Test steel plate thickness and be 20mm.
A1~A4, B1 all use electric arc furnace smelting+AOD refine, hammer cogging after electroslag remelting, Carrying out high-temperature behavior comparison and detection after admittedly holding heat treatment being rolled into steel plate, B2 uses vacuum+electroslag Detect after being rolled into steel plate after becoming ingot, more forged cogging.
As shown in Fig. 3, Fig. 4, Fig. 5, respectively to test and compare the steel plate of alloy and carry out performance detection, Item compared is high temperature tensile properties, antioxygenic property and high temperature endurance performance.From Fig. 3, Fig. 4, figure The contrast of 5 is not it can be seen that alloy of the present invention and comparative alloy have substantially on high temperature tensile properties Gap, but on high temperature oxidation resistance, alloy of the present invention still has preferable resistance to height on 1200 DEG C Temperature oxidation susceptibility, on high temperature endurance performance, alloy of the present invention is suitable with B2, but relatively B1 has substantially Advantage.
Alloy of the present invention has excellent high temperature oxidation resisting and persistently due to its more existing Chlorimet Croop property, and realize ingot processed by electric arc furnace+refine, more existing high performance heat resistant is Ni-based Alloy lumber recovery on producing is greatly improved, simultaneously, it is possible to decrease production cost improves production efficiency, And it is provided that big specification material.Its successful design exploitation application to domestic high-performance special alloy Huge Social and economic benef@will be brought.
Those of ordinary skill in the art is it should be appreciated that above embodiment is intended merely to The bright present invention, and it is not used as limitation of the invention, as long as at the spirit of the present invention In, change, the modification of embodiment described above all will be fallen in the range of claims of the present invention.

Claims (5)

1. a high temperature oxidation resisting nickel-base alloy, it is characterised in that the percentage by weight of its each composition For:
C :≤0.1%, Cr:15~30%, Al:1.0~2.5%, Ti:0.01~1.0%, Si: ≤ 0.3%, Mn :≤0.5%, Mg:0.01~0.05%, B:0.002~0.03%, Zr:0.01~ 0.15%, N:0.01~0.02%, P≤0.010%, S≤0.010%;
Wherein, P+S≤0.015%;
Remaining is Ni and inevitable impurity composition.
2. high temperature oxidation resisting nickel-base alloy as claimed in claim 1, it is characterised in that its each become The percentage by weight divided is:
C:0.02%, Si:0.1%, Mn:0.2%, Cr:15%, Al:1.0%, Ti:1.0%, B:0.03%, Zr:0.10%, P:0.01%, S:0.002%, N:0.01%, Mg:0.05%;
Remaining is Ni and inevitable impurity composition.
3. high temperature oxidation resisting nickel-base alloy as claimed in claim 1, it is characterised in that its each become The percentage by weight divided is:
C:0.1%, Si:0.2%, Mn:0.2%, Cr:20%, Al:2.0%, Ti:0.3%, B:0.02%, Zr:0.10%, P:0.008%, S:0.01%, N:0.015%, Mg:0.03%;
Remaining is Ni and inevitable impurity composition.
4. high temperature oxidation resisting nickel-base alloy as claimed in claim 1, it is characterised in that its each become The percentage by weight divided is:
C:0.05%, Si:0.3%, Mn:0.5%, Cr:25%, Al:2.5%, Ti:0.2%, B:0.003%, Zr:0.03%, P:0.008%, S:0.005%, N:0.02%, Mg: 0.01%;
Remaining is Ni and inevitable impurity composition.
5. high temperature oxidation resisting nickel-base alloy as claimed in claim 1, it is characterised in that its each become The percentage by weight divided is:
C:0.02%, Si:0.3%, Mn:0.4%, Cr:22%, Al:2.3%, Ti:0.2%, B:0.002%, Zr:0.02%, P:0.005%, S:0.002%, N:0.018%, Mg: 0.02%;
Remaining is Ni and inevitable impurity composition.
CN201510012838.7A 2015-01-12 2015-01-12 High temperature oxidation resisting nickel-base alloy Active CN105838925B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107243604A (en) * 2017-06-28 2017-10-13 安徽华飞机械铸锻有限公司 A kind of metal mould cast method
WO2021046929A1 (en) * 2019-09-12 2021-03-18 南京达迈科技实业有限公司 Large-diameter ni-cr rotating target containing trace elements and preparation method therefor
CN116121598A (en) * 2022-12-26 2023-05-16 北京钢研高纳科技股份有限公司 Aging-strengthened superalloy powder for 3D printing and its preparation method and application

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CN102628126A (en) * 2012-05-03 2012-08-08 丹阳恒庆复合材料科技有限公司 Austenite corrosion-resisting nickel-based casting alloy and manufacturing process thereof
CN103173658A (en) * 2011-12-22 2013-06-26 株式会社日立制作所 Nickel based forged alloy, gas turbine member using said alloy and gas turbine using said member

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Publication number Priority date Publication date Assignee Title
US3749612A (en) * 1971-04-06 1973-07-31 Int Nickel Co Hot working of dispersion-strengthened heat resistant alloys and the product thereof
JPS5956556A (en) * 1982-09-25 1984-04-02 Nippon Yakin Kogyo Co Ltd Ni alloy with superior intergranular corrosion resistance and stress corrosion cracking resistance
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CN103173658A (en) * 2011-12-22 2013-06-26 株式会社日立制作所 Nickel based forged alloy, gas turbine member using said alloy and gas turbine using said member
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107243604A (en) * 2017-06-28 2017-10-13 安徽华飞机械铸锻有限公司 A kind of metal mould cast method
WO2021046929A1 (en) * 2019-09-12 2021-03-18 南京达迈科技实业有限公司 Large-diameter ni-cr rotating target containing trace elements and preparation method therefor
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