CN101130844A - High-temperature alloy with low content of cobalt and nickel - Google Patents
High-temperature alloy with low content of cobalt and nickel Download PDFInfo
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- CN101130844A CN101130844A CNA2006101159557A CN200610115955A CN101130844A CN 101130844 A CN101130844 A CN 101130844A CN A2006101159557 A CNA2006101159557 A CN A2006101159557A CN 200610115955 A CN200610115955 A CN 200610115955A CN 101130844 A CN101130844 A CN 101130844A
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- 239000000956 alloy Substances 0.000 title claims abstract description 132
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 130
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 37
- 229910052759 nickel Inorganic materials 0.000 title claims description 22
- 229910017052 cobalt Inorganic materials 0.000 title claims description 14
- 239000010941 cobalt Substances 0.000 title claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
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- 238000012545 processing Methods 0.000 claims description 31
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- 238000002844 melting Methods 0.000 claims description 10
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- 238000005096 rolling process Methods 0.000 claims description 10
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- 238000002360 preparation method Methods 0.000 abstract description 8
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- 238000012360 testing method Methods 0.000 description 30
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- 229910052580 B4C Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 244000137852 Petrea volubilis Species 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
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- 229910000601 superalloy Inorganic materials 0.000 description 2
- 229910002467 CrFe Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
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- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
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- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
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- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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Abstract
The present invention provides a kind of high-temperature resistant alloy with low nickel-cobalt content. Said alloy has good deformability, high toughness and high high-temperature resistance. Said alloy contains 5-7 main elements, and is made up by using CoCrFeNi as basis and adding at least one of Al, Mo and Ti as main element through a certain preparation process. Besides, said invention also provides the concrete steps of said preparation process.
Description
Technical field
The invention relates to a kind of high temperature alloy of low content of cobalt and nickel, especially about synthetic, based on the high temperature alloy of a kind of low content of cobalt and nickel of FCC (face-centered cube) crystallization via the designing institute of multicomponent alloy.
Background technology
Known alloy system serves as main classification with elements such as iron, copper, aluminium, magnesium, titanium, zirconium, lead, zinc, gold and silver.For a long time, the exploitation of known alloy system is the character that principal element (atomic percent is more than at least 50%) and other minor element of arranging in pairs or groups come modified alloy with single metallic element mainly.For example iron alloy, copper alloy, magnesium alloy, titanium alloy etc.Over year, though the development of existing rapidly solidified alloy, mechanical alloy, metal-base composites, the main points that its alloy designs and alloy are selected do not break away from the idea based on a kind of element yet surplus in the of nearly 30.
The research of the amorphous bulk matter alloy material that is risen over year surplus in the of nearly ten, its alloy designs is: (1) two-phase exotic atom correction for semi-diameter is more than 12%; (2) at least three more than the element; (3) very big mixing heat release must be arranged.But according to the document of being delivered over the years, can find that these researchs are principal element with an element still, at least more than 40% atomic ratio, the amorphous alloy of iron-based, titanium base, magnesium base, zirconium base for example.
In view of the exploitation of known alloy system is limited in the framework of one or two principal element, limited the degree of freedom and the space of alloy development virtually.Therefore, the inventor proposes the alloy idea (polynary high-entropy alloy) of innovation from nineteen ninety-five, promptly dispose alloy with five principal elements at least, make the degree of freedom of alloying constituent greatly increase, thereby increase the development of novel crystal structure, microtexture and new capability.Particularly, on thermodynamics, the high entropy under the multicomponent alloy helps the reduction and the stability of system's free energy.So tending to form, high-entropy alloy mixes the solid solution phase of arranging, but not Jie's metallic compound of ordered arrangement, thereby can reduce brittle phenomenon generation.
Because the FCC crystallization has 12 sliding systems, usually has preferable deformability, simultaneously because its intensity is more insensitive to variation of temperature, and the loss of its intensity at high temperature is less, this also is that Ni-based, cobalt-based and iron-based superalloy must be based on the main causes of FCC crystallization.Because secondly the raw materials cost height of cobalt-based is Ni-based, iron-based is the most cheap, and the present invention provides a novel alloy system, can reduce under the cobalt nickel usage quantity, still can be based on the FCC crystal structure, and thereby increase industry utilization widely.
Summary of the invention
The objective of the invention is to utilize the design of multicomponent alloy one low content of cobalt and nickel to be provided and to be main high temperature alloy with the FCC crystallization, this alloy is based on the CoCrFeNi quad alloy and add Al, Mo and Ti is at least a is principal element and is configured to multicomponent alloy, wherein each elements atomic percentage of Co and Ni is all between 20% to 35%, each elements atomic percentage of Cr and Fe is all between 12.5% to 20%, and the summation of Co, Cr, Fe and Ni atomic percent surpasses 65%.And the summation of the atomic percent of Al, Mo or Ti is between 5% to 25%.In addition, also can add the characteristic that minor elements such as Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, Y, Zr improve alloy, but the summation of the atomic percent of interpolation minor element must not surpass 10%.
This alloy system can (Co, Cr, Fe, Ni)
xM
yN
zComposition represented, wherein the M element can be selected from Al, Mo and Ti at least a, the N element is a minor element, as it is at least a to be selected from Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, Y, Zr etc., calculate with atomic percent, x 〉=65%, 5≤y≤25% and 0＜z≤10%, wherein each elements atomic percentage of Co and Ni is all between 20% to 35%, and Cr and each elements atomic percentage of Fe are all between 12.5% to 20%.Traditional fusion castings such as this alloy can the nichrome wire heating method, induction heating, vacuum arc melting method form, can also utilize synthetic alloys such as rapid solidification method, machine-alloying and powder metallurgic method, and can use for follow-up forging processing, metal processing treatment such as homogenize thermal treatment and rolling and processing.
According to an embodiment of the present invention, utilize the design of above-mentioned multicomponent alloy to prepare high-entropy alloy test piece in 11, with Co
1.5CrFeNi
1.5Be base alloy, add an amount of Al, Mo, Ti, via all having good alloy property after the vacuum arc melting casting, wherein the interpolation of Al, Mo, Ti is to this alloy system Co
1.5CrFeNi
1.5Have strengthening effect in various degree, obviously the effect of Ti is best, is Mo secondly, is Al secondly again.
According to an embodiment of the present invention, with Co
1.5CrFeNi
1.5Ti
0.5Test piece forge processing, after homogenize thermal treatment and the rolling and processing, observe the microstructure of test piece under various states and the variation of hardness.The result shows that this alloy has the ability of superior heatproof characteristic and work hardening.
According to an embodiment of the present invention, utilize the design of above-mentioned multicomponent alloy to prepare other 11 kinds of high-entropy alloy test pieces, with Co
2CrFeNi
2Be base alloy, add an amount of Al, Mo, Ti, via all having good alloy property after the vacuum arc melting casting, wherein the interpolation of Al, Mo, Ti is to this alloy system Co
2CrFeNi
2Have strengthening effect in various degree, obviously the effect of Ti is best, is Mo secondly, is Al secondly again.
According to an embodiment of the present invention, with Co
2CrFeNi
2Ti
0.Processing is forged in 5 test piece, after homogenize thermal treatment and the rolling and processing, observe the hardness of test piece under each state and the variation of microstructure.The result shows that this alloy has the ability of superior heatproof characteristic and work hardening.
According to an embodiment of the present invention, utilize design preparation 18 kinds of high-entropy alloy test pieces in addition of above-mentioned multicomponent alloy, wherein add an amount of minor element such as Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, Y, Zr is at least a with the preparation multicomponent alloy.The interpolation total amount of minor element is no more than atomic percent 10%, and the hardness value of alloy test piece is because of the element that adds difference to some extent.Therefore, can utilize different additions to adjust hardness, ductility and processibility, to be fit to the application under application, the especially thermal structure under the varying strength.
In addition, according to still another embodiment of the invention, this alloy also can carry out hardening treatment with the high-temperature aging method after through the vacuum arc casting.
As above-mentioned, this polynary high-entropy alloy be belong to can process, analyzable alloy material, and be one to have the alloy of well processed sclerosis, high-temperature aging sclerosis and high-temperature stability.
Description of drawings
Fig. 1 is according to the alloy preparation of the embodiment of the invention and the schema of processing treatment.
Embodiment
Hereinafter with reference to illustrating embodiments of the invention to promote to thorough understanding of the present invention.Wherein use suitable, the identical identical characteristic of reference symbol representative.Yet, should understand only property and nonrestrictive example as an illustration at the inferior embodiment that proposes.Therefore, the present invention is not limited in the embodiment that is proposed, and more comprises to be familiar with any variation and the coordinator thereof that this technician understands.
About the hardness of alloy test piece, be to utilize Vickers' hardness experimental machine (MATSUZAWA SEIKI MV-1) to be measured in an embodiment of the present invention.Before the measurement, the surface of test piece is measured with hardness tester after silicon carbide (SiC) the sand paper grinding leveling of preface with #80, #180, #240, #400, #600, #800, #1200 successively again.Institute's application of load is 5kgf during measurement, and duration of load application is 15 seconds, and pin speed is 50 μ m/s under the diamond tool.The hardness value of seven different positionss is all measured in each test piece, with middle five mean values on average as the hardness of this test piece.
In addition, observing about microstructure is to utilize water-cooled sharpening machine cutting test piece is arranged, and makes test piece not cut the microstructure on surface because of the temperatures involved of cutting.Preface is with the SiC sand paper grinding leveling of #180, #240, #400, #600, #800, #1200, #2000, #4000 successively in test piece after the cutting, and the diamond suspension with 3 μ m polishes again.Test piece after the polishing is with chloroazotic acid (HNO
3+ 3HCl) be the etching solution etch, carry out microstructure with opticmicroscope (OM) and JEOL-5410 scanning electronic microscope (SEM) again and observe, and carry out composition analysis with EDS (energy dispersive analyser).
The evaluation of wide area crystalline structure phase is to get about 1 * 15 * 15mm test piece to carry out X light diffracting analysis in addition, and this is to use RIGAKU ME510-FM2X x ray diffractometer x, carries out the X ray ionization meter with Cu target X ray light source.Operating voltage is 30kV, and actuating current is 20mA, and sweep limit is by 20 to 100 degree, and sweep velocity is 4degrees/min.
Embodiment one:
Table 1 is the selected alloy composition of present embodiment, and the test piece label is HE1 to HE11, with Co
1.5CrFeNi
1.5Be base alloy, (Vickers' hardness of alloy is HV113, is the FCC crystalline structure) added an amount of Al, Ti, Mo and prepared multicomponent alloy.The material purity that disposes used element is all more than 99%.Indivedual fundamental characteristics of the principal element of alloying constituent of the present invention that table 2 is classified as comprise nucleidic mass, size, fusing point, boiling point, density, crystalline structure and crystalline structure conversion temp.
Table 1: the composition numbering of alloy: (right seven hurdles are atomic percent)
| Numbering | Composition (representing) with atomic ratio | Co | Cr | Fe | Ni | Al | Ti | Mo |
| HE1 HE2 HE3 HE4 HE5 HE6 HE7 HE8 | Co 1.5CrFeNi 1.5Al 0.5 Co 1.5CrFeNi 1.5Ti 0.5 Co 1.5CrFeNi 1.5Mo 0.5 Co 1.5CrFeNi 1.5Al Co 1.5CrFeNi 1.5Ti Co 1.5CrFeNi 1.5Mo Co 1.5CrFeNi 1.5Al 0.5Ti 0.5 Co 1.5CrFeNi 1.5Al 0.5Mo 0.5 | 27.3 27.3 27.3 25.0 25.0 25.0 25.0 25.0 | 18.2 18.2 18.2 16.7 16.7 16.7 16.7 16.7 | 18.2 18.2 18.2 16.7 16.7 16.7 16.7 16.7 | 27.3 27.3 27.3 25.0 25.0 25.0 25.0 25.0 | 9.0 0 0 16.6 0 0 8.3 8.3 | 9.0 0 0 16.6 0 8.3 0 | 0 9.0 0 0 16.6 0 8.3 |
| HE9 HE10 HE11 | Co 1.5CrFeNi 1.5Ti 0.5Mo 0.5 Co 1.5CrFeNi 1.5Al 0.5Ti 0.5Mo 0.5 Co 1.5CrFeNi 1.5Al 0.25Ti 0.5Mo 0.25 | 25.0 23.1 25.0 | 16.7 15.4 16.7 | 16.7 15.4 16.7 | 25.0 23.1 25.0 | 0 7.7 4.15 | 8.3 7.7 8.3 | 8.3 7.6 4.15 |
Table 2: the fundamental characteristics of alloying element
| Element | Al | Ti | Co | Cr | Fe | Mo | Ni |
| Nucleidic mass (g/mole) | 26.98 | 47.867 | 58.93 | 52.00 | 55.85 | 95.94 | 58.69 |
| Atomic radius (A) | 1.18 | 1.76 | 1.52 | 1.66 | 1.56 | 1.9 | 1.49 |
| Fusing point (℃) | 660 | 1668 | 1495 | 1907 | 1538 | 2623 | 1455 |
| Boiling point (℃) | 2519 | 3287 | 2927 | 2671 | 2861 | 4639 | 2913 |
| Density (g/cm 3) | 2.70 | 4.053 | 8.9 | 7.14 | 7.87 | 10.28 | 8.91 |
| Crystalline structure (low temperature) | FCC | HCP | HCP | BCC | BCC | BCC | FCC |
| Crystalline structure (high temperature) | FCC | BCC | FCC | FCC | FCC、BCC | BCC | FCC |
| The crystalline structure conversion temp (℃) | - | - | 417 | 1840 | 910 1390 | - | - |
Fig. 1 is alloy preparation according to an embodiment of the invention, processing treatment flow process.As shown in Figure 1, can adopt vacuum arc melting furnace to come molten alloy in the present embodiment, and can supply the usefulness of follow-up forging processing, the thermal treatment that homogenizes, rolling and processing and timeliness hardening treatment.Carry out hardness measurement, X light diffracting analysis, microstructure observation and composition analysis then.The pure metal particles proportioning that earlier gross weight about 50 is restrained during melting places on the water cooled copper mould, covers the loam cake of stove, and extracting vacuum then feeds pure argon to 0.2atm to 0.01atm.For fear of a large amount of oxidations of alloy, repeat the aforesaid gas replenishment process three times of bleeding again after, the side carries out melting and handles, wherein the melting electric current is 500 amperes.After metal block has dissolved evenly and has treated its cooling, the metal block turn-over is carried out melting again, several makes its cooled and solidified form foundry goods or ingot casting till definite all alloying elements have all dissolved and mixed then so repeatedly.
According to 11 kinds of prepared alloys of table 1, its crystalline structure and hardness are as shown in table 3, all have good alloy property.Particularly, by table 3 as seen, the interpolation of Al, Mo, Ti is to this alloy system Co
1.5CrFeNi
1.5(hardness value is HV113) has strengthening effect in various degree, and obviously the effect of Ti is best, is Mo secondly, is Al secondly again.In addition, when the addition of this element increased, its hardness also increased.Alloy part can form BCC (body-centered cube) phase, but main phase still is the FCC crystalline structure, therefore utilizes different additions, can adjust hardness, ductility and processibility etc., to be fit to the application under application, the especially thermal structure under the varying strength.
The crystalline structure and the hardness (HV) of table 3:HE1-HE11 alloy-steel casting
| Numbering | Composition (representing) with atomic ratio | Crystalline structure | Hardness |
| HE1 HE2 HE3 HE4 HE5 HE6 HE7 HE8 HE9 HE10 HE11 | Co 1.5CrFeNi 1.5Al 0.5 Co 1.5CrFeNi 1.5Ti 0.5 Co 1.5CrFeNi 1.5Mo 0.5 Co 1.5CrFeNi 1.5Al Co 1.5CrFeNi 1.5Ti Co 1.5CrFeNi 1.5Mo Co 1.5CrFeNi 1.5Al 0.5Ti 0.5 Co 1.5CrFeNi 1.5Al 0.5Mo 0.5 Co 1.5CrFeNi 1.5Ti 0.5Mo 0.5 Co 1.5CrFeNi 1.5Al 0.5Ti 0.5Mo 0.5 Co 1.5CrFeNi 1.5Al 0.25Ti 0.5Mo 0.25 | FCC FCC FCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC | 136 378 193 277 581 394 385 200 417 561 383 |
Embodiment two
The alloy preparation as shown in Figure 1 and the flow process of processing treatment are with the HE2 alloy Co among the embodiment one
1.5CrFeNi
1.5Ti
0.5Test piece insert 1000 ℃ of High Temperature Furnaces Heating Apparatuss insulation 15 minutes, then take out use the pneumatic type exercise machine (model:: OT-1521280) carry out forge hot, loading 250kg, amount of finish are 40%.Then, will forge test piece and insert in the heat treatment furnace, and after the processing that homogenizes in 1100 ℃, 24 hours, carry out the cold and two kinds of cooling process of shrend of stove respectively, the hardness in each stage of gained is as shown in table 4, and the hardness after the forging promotes about 30%.The stove that homogenizes is chill, and degree descends, but shrend is slightly high, can find that thus this alloy does not present 1100 ℃ of hot mastication phenomenons, shows that this alloy has superior heatproof characteristic.And the crystal structure of each state all still is single FCC phase through X light diffracting analysis.
Table 4:Co
1.5CrFeNi
1.5Ti
0.5Alloy is through forging, high temperature forging and the hardness (HV) that homogenizes
| Alloy | Casting | High temperature forging | The stove that homogenizes is cold | Shrend homogenizes |
| Co 1.5CrFeNi 1.5Ti 0.5 | 378 | 488 | 313 | 392 |
Then, with the alloy test piece (Co of the stove deepfreeze that homogenizes
1.5CrFeNi
1.5Ti
0.5), (model: DBR250) carry out rolling and processing and handle to observe the variation of hardness, amount of finish is respectively 0%, 5%, 15%, 30%, 80% to utilize double formula roller press.The gained result is as shown in table 5, and the amount of finish that this alloy test piece is handled along with rolling and processing increases and tangible work hardening is arranged, and processing back hardness all rolls up, and wherein processes 30% back hardness 1.78 times before promptly increasing to processing approximately.Thereby demonstrate the characteristic that this alloy has good workhardness.Show Co via X light diffracting analysis
1.5CrFeNi
1.5Ti
0.5Alloy is along with amount of finish increases, and the diffraction peak foundry goods of FCC descends, this be because alloy after processing, lattice can produce bigger distorting, and then makes X-ray produce a large amount of diffuse effect.
Table 5:Co
1.5CrFeNi
1.5Ti
0.5The hardness (HV) of alloy after different amount of finish roll extrusion
| Amount of finish | 0％ | 5％ | 15％ | 30％ | 80％ |
| Hardness | 313 | 467 | 452 | 558 | 545 |
Embodiment three
Table 6 is the selected alloy compositions of present embodiment, and test piece number is HE12 to HE22, with Co
2CrFeNi
2For base alloy (Vickers' hardness of alloy is HV108, is the FCC crystalline structure), add an amount of Al, Ti, Mo and prepare multicomponent alloy.The material purity that disposes used element is all more than 99%.
The composition and the numbering of table 6:HE12-HE22 alloy: (right seven hurdles are atomic percent)
| Numbering | Composition (atomic ratio is represented) | Co | Cr | Fe | Ni | Al | Ti | Mo |
| HE12 | Co 2CrFeNi 2Al 0.5 | 30.8 | 15.4 | 15.4 | 30.8 | 7.6 | 0 | 0 |
| HE13 HE14 HE15 HE16 HE17 HE18 HE19 HE20 HE21 HE22 | Co 2CrFeNi 2Ti 0.5 Co 2CrFeNi 2Mo 0.5 Co 2CrFeNi 2Al Co 2CrFeNi 2Ti Co 2CrFeNi 2Mo Co 2CrFeNi 2Al 0.5Ti 0.5 Co 2CrFeNi 2Al 0.5Mo 0.5 Co 2CrFeNi 2Ti 0.5Mo 0.5 Co 2CrFeNi 2Al 0.5Ti 0.5Mo 0.5 Co 2CrFeNi 2Al 0.25Ti 0.5Mo 0.25 | 30.8 30.8 28.6 28.6 28.6 28.6 28.6 28.6 26.7 28.6 | 15.4 15.4 14.3 14.3 14.3 14.3 14.3 14.3 13.3 14.3 | 15.4 15.4 14.3 14.3 14.3 14.3 14.3 14.3 13.3 14.3 | 30.8 30.8 28.6 28.6 28.6 28.6 28.6 28.6 26.7 28.6 | 0 0 14.2 0 0 7.1 7.1 0 6.7 3.5 | 7.6 0 0 14.2 0 7.1 0 7.1 6.7 7.2 | 0 7.6 0 0 14.2 0 7.1 7.1 6.6 3.5 |
The crystalline structure and the hardness of the 11 kinds of alloys (as shown in table 6) in the present embodiment are as shown in table 7, all have good alloy property.Particularly, by table 7 as seen, the interpolation of Al, Mo, Ti is to this alloy system Co
2CrFeNi
2(hardness value is HV108) has strengthening effect in various degree, and obviously the effect of Ti is best, is Mo secondly, is Al secondly again.In addition, when the addition of this element increased, its hardness also increased.Alloy part can form the BCC phase, but main phase still is the FCC crystalline structure, therefore utilizes different additions, can adjust hardness, ductility and processibility etc., to be fit to the application under application, the especially thermal structure under the varying strength.
The crystalline structure and the hardness (HV) of table 7:HE12-HE22 alloy-steel casting
| Numbering | Composition (representing) with atomic ratio | Crystalline structure | Hardness |
| HE12 HE13 HE14 HE15 HE16 | Co 2CrFeNi 2Al 0.5 Co 2CrFeNi 2Ti 0.5 Co 2CrFeNi 2Mo 0.5 Co 2CrFeNi 2Al Co 2CrFeNi 2Ti | FCC FCC FCC FCC+BCC FCC+BCC | 124 340 170 230 456 |
| HE17 HE18 HE19 HE20 HE21 HE22 | Co 2CrFeNi 2Mo Co 2CrFeNi 2Al 0.5Ti 0.5 Co 2CrFeNi 2Al 0.5Mo 0.5 Co 2CrFeNi 2Ti 0.5Mo 0.5 Co 2CrFeNi 2Al 0.5Ti 0.5Mo 0.5 Co 2CrFeNi 2Al 0.25Ti 0.5Mo 0.25 | FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC | 236 356 180 316 376 349 |
Embodiment four:
With the HE13 alloy Co among the embodiment three
2CrFeNi
2Ti
0.5Test piece insert 1000 ℃ of High Temperature Furnaces Heating Apparatuss insulation 15 minutes, then take out and use the pneumatic type swaging machine (model: OT-1521280) carry out forge hot, loading 250kg, amount of finish are 40%.Then, will forge test piece and insert in the heat treatment furnace, and after the processing that homogenizes in 1100 ℃, 24 hours, carry out the cold and two kinds of cooling process of shrend of stove respectively, the hardness in each stage of gained is as shown in table 8, and the hardness after the forging promotes about 28%.The stove that homogenizes is chill, and degree rises, but shrend is constant approximately, can find that thus this alloy does not present 1100 ℃ of hot mastication phenomenons, shows that this alloy has superior heatproof characteristic.And the crystal structure of each state all still is single FCC phase through X light diffracting analysis.
Table 8:Co
2CrFeNi
2Ti
0.5Alloy is through casting, high temperature forging and the hardness (HV) that homogenizes
| Alloy | Casting | High temperature forging | The stove that homogenizes is cold | Shrend homogenizes |
| Co 2CrFeNi 2Ti 0.5 | 339 | 421 | 403 | 328 |
Then, with the alloy test piece (Co of the stove deepfreeze that homogenizes
2CrFeNi
2Ti
0.5), (model: DBR250) carry out rolling and processing and handle to observe the variation of hardness, amount of finish is respectively 0%, 5%, 15%, 30%, 70% to utilize double formula roller press.The gained result is as shown in table 9, and the amount of finish that this alloy test piece is handled along with rolling and processing increases and tangible work hardening is arranged, and processing back hardness all rolls up, and wherein processes 30% back hardness 1.57 times before promptly increasing to processing approximately.Thereby demonstrate the characteristic that this alloy has good work hardening.Show Co via X light diffracting analysis
2CrFeNi
2Ti
0.5Alloy is along with amount of finish increases, and the diffraction peak of FCC descends gradually, this be because alloy after processing, lattice can produce bigger distorting, and then makes X-ray produce a large amount of diffuse effect.
Table 9:Co
2CrFeNi
2Ti
0.5The hardness (HV) of alloy after different amount of finish roll extrusion
| Amount of finish | 0％ | 5％ | 15％ | 30％ | 70％ |
| Hardness | 328 | 335 | 416 | 515 | 566 |
Embodiment five:
Table 10 is the selected alloy compositions of present embodiment, and test piece number is HE23 to HE40.These 18 kinds of alloys are to be that HE12-20 (as shown in table 6) is a base alloy with HE1-HE9 (as shown in table 1), add an amount of minor element such as Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, Y, Zr etc. are at least a with the preparation multicomponent alloy.The material purity that disposes used element is all more than 99%.
The composition and the numbering of table 10:HE23-HE40 alloy: (right element hurdle is an atomic percent)
| Label | Composition (representing) with atomic ratio | Co | Cr | Fe | Ni | Al | Ti | Mo | Other elements |
| HE23 HE24 HE25 HE26 HE27 HE28 HE29 HE30 | Co 1.5CrFeNi 1.5Al 0.5Ag 0.2 Co 1.5CrFeNi 1.5Ti 0.5B 0.1C 0.1 Co 1.5CrFeNi 1.5Mo 0.5S 0.2 Co 1.5CrFeNi 1.5AlCu 0.2Mn 0.3 Co 1.5CrFeNi 1.5TiNb 0.1V 0.2 Co 1.5CrFe Ni 1.5MoNb 0.1V 0.2W 0.3 Co 1.5CrFeNi 1.5Al 0.5Ti 0.5 Ta 0.2Zr 0.1 Co 1.5CrFeNi 1.5Al 0.5Mo 0.5 V 0.2Y 0.1 | 26.3 26.3 26.3 23.1 23.8 22.7 23.8 23.8 | 17.5 17.5 17.5 15.4 15.9 15.1 15.9 15.9 | 17.5 17.5 17.5 15.4 15.9 15.1 15.9 15.9 | 26.3 26.3 26.3 23.1 23.8 22.7 23.8 23.8 | 8.9 0 0 15.4 0 0 7.9 7.9 | 0 8.9 0 0 15.8 0 7.9 0 | 0 0 8.9 0 0 15.3 0 7.9 | Ag：3.5％ B：1.75％， C：1.75％ Si：3.5％ Cu：3.0％， Mn：4.6％ Nb：1.6％， V：3.2％ Nb：1.5％， V：3％， W：4.6％ Ta：3.2％， Zr：1.6％ V：3.2％， Y：1.6％ |
| HE31 HE32 HE33 HE34 HE35 HE36 HE37 HE38 HE39 HE40 | Co 1.5CrFeNi 1.5Ti 0.5Mo 0.5 Ta 0.1Y 0.1 Co 2CrFeNi 2Al 0.5Ag 0.2 Co 2CrFeNi 2Ti 0.5B 0.1C 0.1 Co 2CrFeNi 2Mo 0.5Si 0.2 Co 2CrFeNi 2AlCu 0.2Mn 0.3 Co 2CrFeNi 2TiNb 0.1V 0.2 Co 2CrFeNi 2MoNb 0.1V 0.2W 0.3 Co 2CrFeNi 2Al 0.5Ti 0.5 Ta 0.2Zr 0.1 Co 2CrFeNi 2Al 0.5Mo 0.5 V 0.2Y 0.1 Co 2CrFeNi 2Ti 0.5Mo 0.5 Ta 0.1Y 0.1 | 24.2 29.8 29.8 29.8 26.7 27.4 26.3 27.4 27.4 27.8 | 16.1 14.9 14.9 14.9 13.3 13.7 13.2 13.7 13.7 13.9 | 16.1 14.9 14.9 14.9 13.3 13.7 13.2 13.7 13.7 13.9 | 24.2 29.8 29.8 29.8 26.7 27.4 26.3 27.4 27.4 27.8 | 0 7.4 0 0 13.3 0 0 6.8 6.8 0 | 8.1 0 7.4 0 0 13.7 0 6.8 0 6.9 | 8.1 0 0 7.4 0 0 13.2 0 6.8 6.9 | Ta：1.6％， Y：1.6％ Ag：3％ B：1.5％， C：1.5％ Si：3％ Cu：2.7％， Mn：4.0％ Nb：1.4％， V：2.7％ Nb：1.3％， V：2.6％， W：3.9％ Ta：2.8％， Zr：1.4％ V：2.8％， Y：1.4％ Ta：1.4％， Y：1.4％ |
The crystalline structure and the hardness of the 18 kinds of alloys (as shown in table 10) in the present embodiment are as shown in table 11, all have good alloy property.Particularly, by table 11 as seen, add the atomic percent total amount surpass a small amount of minor element of 10% such as Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, when Y, Zr etc. are at least a, hardness value can be because of the element that added difference to some extent.In addition, table 3, table 7 and table 11 are compared, can find out except that the interpolation of Ag and Cu, the interpolation of other minor elements all has the hardness castering action basically.Though the interpolation of part element can increase the formation of BCC phase, main still is the FCC crystalline structure mutually, therefore, utilizes different additions, can adjust hardness, ductility and processibility etc., to be fit to the application under application, the especially thermal structure under the varying strength.
The crystalline structure and the hardness (HV) of table 11:HE23-HE40 alloy-steel casting
| Numbering | Composition (representing) with atomic ratio | Crystalline structure | Hardness |
| HE23 HE24 HE25 HE26 HE27 HE28 HE29 HE30 HE31 HE32 HE33 HE34 HE35 HE36 HE37 HE38 HE39 HE40 | Co 1.5CrFeNi 1.5A l0.5Ag 0.2 Co 1.5CrFeNi 1.2Ti 0.5B 0.1C 0.1 Co 1.5CrFeNi 1.5Mo 0.5Si 0.2 Co 1.5CrFeNi 1.5AlCu 0.2Mn 0.3 Co 1.5CrFeNi 1.5TiNb 0.1V 0.2 Co 1.5CrFeNi 1.5MoNb 0.1V 0.2W 0.3 Co 1.5CrFeNi 1.5Al 0.5Ti 0.5Ta 0.2Zr 0.1 Co 1.5CrFeNi 1.5Al 0.5Mo 0.5V 0.2Y 0.1 Co 1.5CrFeNi 1.5Ti 0.5Mo 0.5Ta 0.1Y 0.1 Co 2CrFeNi 2Al 0.5Ag 0.2 Co 2CrFeNi 2Ti 0.5B 0.1C 0.1 Co 2CrFeNi 2Mo 0.5S 0.2 Co 2CrFeNi 2AlCu 0.2Mn 0.3 Co 2CrFeNi 2TiNb 0.1V 0.2 Co 2CrFeNi 2MoNb 0.1V 0.2W 0.3 Co 2CrFeNi 2Al 0.5Ti 0.5Ta 0.2Zr 0.1 Co 2CrFeNi 0.5Mo 0.5V 0.2Y 0.1 Co 2CrFeNi 2Ti 0.5Mo 0.5Ta 0.1Y 0.1 | FCC FCC+ boron-carbide phase FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC FCC+ boron-carbide phase FCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC FCC+BCC | 125 424 231 257 715 732 590 271 626 110 356 177 201 529 580 556 229 503 |
In addition, according to another embodiment of the present invention, for example, get a Co
1.5CrFeNi
1.5Ti
0.5The alloy test piece is carried out hardening treatment via after the vacuum arc melting casting with the high-temperature aging method.This casting attitude test piece is inserted in the heat treatment furnace, respectively with 400 ℃, 600 ℃, 800 ℃ timeliness 1hr, 2hr, 5hr, 10hr.The result is as shown in table 12, under 800 ℃ condition, can be observed rare high-temperature aging hardening phenomenon, and timeliness 5hr can make hardness of alloy rise to 513HV from 378HV.After through the 10hr timeliness, hardness of alloy becomes 1.33 times before about timeliness.
Table 12: aging temp and time are to the changing value of alloy rigidity
Comprehensive the above, can understand alloy system of the present invention can (Co, Cr, Fe, Ni)
xM
yN
zComposition represented, wherein the M element can be selected from Al, Mo and Ti at least a, the N element is that minor element such as Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, Y, Zr etc. are at least a, calculate with atomic percent, x 〉=65%, 5≤y≤25% and 0＜z≤10%, wherein each elements atomic percentage of Co and Ni is all between 20% to 35%, and Cr and each elements atomic percentage of Fe are all between 12.5% to 20%.This alloy system under as-cast condition based on the FCC crystal structure mutually, on crystallography,, be easy to the distortion of sliding, so have suitable ductility usually because FCC has 12 sliding systems mutually.In addition, the intensity of FCC phase is more insensitive to temperature, at high temperature loss of strength is less, so alloy of the present invention can provide different strong hardness, no matter in room-temperature applications or thermal structure application, can be at varying strength and ductile requirement, by the adjustment of composition, and obtain the alloy of appropriate characteristics.In addition, alloy system of the present invention contain respectively Cr and Co, Ni each at least atomic percent be more than 12.5% and 20%, the existence of this element all has suitable load-carrying capacity for erosion resistance and oxidation-resistance, can both provide suitable resistivity under the environment of corrosive environment and high temperature oxidation.Moreover, because Co content is lower, be no more than 35%, for the Co base alloy (its Co content is more than at least 50%) of costliness, its cost can reduce relatively.Therefore the present invention utilizes the design of multicomponent alloy, has developed the alloy system of novelty, progressive and tool industrial utilization.
In addition, be familiar with handling and hardening treatment as the processing of the forging in the processing treatment step of Fig. 1, the thermal treatment that homogenizes, rolling and processing among the embodiment that this operator should be appreciated that, only as exemplary and be not limited to the order of model shown here, for example, can implement wherein a kind of or its combination separately.Also promptly carry out required flow process or processing under the effect of the present invention not hindering, and exactly so to implement the present invention in whole processing that this was proposed.
Though one exemplary embodiment of the present invention below only is described in detail in detail, in every case being familiar with this operator should be appreciated that: above-mentioned explanation only is descriptive and non-limiting, under the situation that does not break away from novel teaching of the present invention and advantage, can carry out various modifications according to the foregoing description.Therefore, all these type of modifications should be considered as comprising in the patent category of the present invention.
Claims (7)
1. the high temperature alloy of a low content of cobalt and nickel, and the consisting of of this alloy (Co, Cr, Fe, Ni)
xM
yN
z, wherein: (Co, Cr, Fe, Ni) shared atomic percent is represented with X, X 〉=65%, wherein each elements atomic percentage of Co and Ni is all between 20% to 35%, and Cr and each elements atomic percentage of Fe are all between 12.5% to 20%;
The shared atomic percent of M element is represented with Y, 5≤Y≤25%, and this M element be selected from Al, Mo and Ti at least a;
The shared atomic percent of N element is represented with Z, 0＜Z≤10%, this N element be selected from Ag, B, C, Cu, Mn, Nb, Ta, Si, V, W, Y, Zr are at least a.
2. the high temperature alloy of low content of cobalt and nickel according to claim 1, wherein this alloy is to form with the founding of vacuum arc melting method.
3. the high temperature alloy of low content of cobalt and nickel according to claim 1 and 2, wherein this alloy is based on the FCC crystallization phases.
4. the high temperature alloy of low content of cobalt and nickel according to claim 1 and 2, wherein this alloy is via forging processing treatment.
5. the high temperature alloy of low content of cobalt and nickel according to claim 1 and 2, this alloy is via the thermal treatment that homogenizes.
6. the high temperature alloy of low content of cobalt and nickel according to claim 1 and 2, this alloy is to handle via rolling and processing.
7. the high temperature alloy of low content of cobalt and nickel according to claim 1 and 2, wherein this alloy is via hardening treatment.
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