CN108385010B - Cobalt-based high-temperature alloy with low density and high structure stability and preparation method thereof - Google Patents
Cobalt-based high-temperature alloy with low density and high structure stability and preparation method thereof Download PDFInfo
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Abstract
A novel gamma' phase strengthened cobalt-based high-temperature alloy with low density and high structure stability and a preparation method thereof belong to the technical field of design and development of new materials. The chemical components are as follows by atomic percent: 5-11% of Al, 0.01-3% of W, 20-35% of Ni, 8-18% of Cr, 1-6% of Mo, 0.01-1% (optional one of Y/Ce/La), 0.01-1% of Si, 0.01-1% of B, 0.01-1% of C, 0.01-1% of Zr, 0.01-1% of Hf, 0-2% of Ta, 0-4% of Ti, 0-4% of Fe, 0-4% of Nb and the balance of Co. The designed alloy components reasonably optimize W, Mo, Si and Y/La/Ce elements, so that the alloy density can be obviously reduced, and the high-temperature performance of the alloy is improved; the developed smelting process can avoid the phenomena of burning loss of low-melting-point elements and uneven melting of high-melting-point elements, and improve the accuracy and uniformity of chemical components of the cast ingot; compared with the similar deformation cobalt-based high-temperature alloy, the developed alloy has lower density and higher stability of medium-temperature structure performance, and is an excellent deformation cobalt-based high-temperature structural material.
Description
The technical field is as follows:
the invention belongs to the field of design and development of new materials, and particularly provides a component of a gamma' phase strengthened cobalt-based high-temperature alloy with low density and high structure stability and a preparation method thereof.
Background art:
compared with nickel-based high-temperature alloy, the cobalt-based high-temperature alloy has excellent heat corrosion resistance, heat fatigue resistance and welding performance, and is a material with important application prospect on hot end parts such as aviation and rocket engine combustion chambers, guide vanes and the like. In particular, the discovery of gamma prime strengthened Co-Al-W based alloys opens a new avenue for the development of novel cobalt-based superalloys [ Sato J, Omori T, Oikawa K, et Al cobalt-base high-temperature alloys [ J ] Science,2006,312(5770):90-1 ].
The research and development time of novel gamma' phase strengthened cobalt-based high-temperature alloy is short, related research is limited, the research mainly focuses on the influence of alloy elements on the structure performance of the cobalt-based high-temperature alloy, no serial alloy grades are formed, particularly, the deformation cobalt-based high-temperature alloy is formed, and only Neumeier subject group and British Dye subject group in Germany have conducted related research so far. Neumeier et al prepared a high-performance novel wrought cobalt-based superalloy by a cast-rolling method, which has a larger hot working interval than that of a hard-to-deform nickel-based superalloy U720Li, and has a yield strength higher than that of a U720Li alloy [ Neumeier S, Fr ] at a temperature of 800 ℃ or highereund L P,M.Novel wroughtγ/γ′cobalt base superalloyswith high strength and improved oxidation resistance[J].Scripta Materialia,2015,109:104-107](ii) a Dye et al prepared a novel wrought cobalt-based Superalloy by powder metallurgy, which had similar yield strength to MarM247 and even higher strength at temperatures above 750 [ [ Knop M, MulveyP, Ismail F, et al.A. New Polycrystalline Co-Ni Superalloy [ J ]].JOM,2014,66(12):2495-2501.]。
However, the novel Co-Al-W-based alloys developed so far have a high alloy density, even higher than 9.0g/cm, due to the element content of 5 at% to 10 at% W3While the density of the traditional wrought nickel-base superalloy Wasploy is only 8.2g/cm3. The defect of higher density of the novel cobalt-based high-temperature alloy becomes one of important factors limiting the application of the novel cobalt-based high-temperature alloy on hot end components of aviation and rocket engines. Therefore, reducing the density of novel cobalt-based superalloys is one of the keys to the practical application of such alloys. On the premise of ensuring the stable structure performance of the alloy, the reasonable substitution of W element is the most effective way for reducing the density of the cobalt-based high-temperature alloy.
The invention content is as follows:
the invention aims to reduce the density of the novel cobalt-based high-temperature alloy, and develops a novel gamma' phase deformation cobalt-based high-temperature alloy with low density and high structural property stability by selecting and optimizing alloy elements and formulating a reasonable preparation process.
The technical scheme of the invention is as follows:
a cobalt-based high-temperature alloy with low density and high structure stability comprises the following chemical components in atomic percent: 5-11% of Al, 0.01-3% of W, 20-35% of Ni, 8-18% of Cr, 1-6% of Mo, 0.01-1% (optional one of Y/Ce/La), 0.01-1% of Si, 0.01-1% of B, 0.01-1% of C, 0.01-1% of Zr, 0.01-1% of Hf, 0-2% of Ta, 0-4% of Ti, 0-4% of Fe, 0-4% of Nb and the balance of Co.
The preparation process of the cobalt-based high-temperature alloy with low density and high structure stability comprises the process of intermediate alloy smelting and alloy smelting, and mainly comprises the following steps of:
(1) considering high-melting-point elements such as W, Mo, Ta, Nb and the like, the Co-Mo-W-Ta-Nb intermediate alloy is firstly smelted, the melting point of the alloy is reduced, and the phenomenon that the high-melting-point alloy is insufficiently melted in the smelting process is prevented. Meanwhile, the alloy elements with lower content, such as: si, B, C, Zr, Hf, Y/Ce/La, etc., are added together with the master alloy to increase the homogeneity of these low elements.
(2) Simple substances of alloy elements except Al and Ti elements, including Ni, Cr, Fe and the like, are put into a crucible together with the intermediate alloy, and Al and Ti elements which are easy to oxidize are put into a hopper so as to be added in the smelting process.
(3) Smelting in a vacuum induction furnace with the vacuum degree lower than 5 × 10-2When Pa is reached, the raw material is heated by low-power electric power transmission to remove the adhering gas, and the vacuum is continuously pumped to 1 × 10-2And when Pa is needed, rapidly heating to 1500-1600 ℃ with high power, preserving heat for 10 minutes, then reducing the temperature to 1300-1400 ℃, preserving heat for 5 minutes, adding Al and Ti elements in a hopper, immediately and rapidly heating to 1500-1600 ℃, preserving heat for 10-15 minutes, and then pouring to prepare the cobalt-based high-temperature alloy ingot.
The invention has the advantages that:
(1) the invention comprehensively considers the comprehensive influence of each element on the cost, density and structure performance of the novel cobalt-based high-temperature alloy during component design, particularly carefully selects and optimizes W, Mo, Si and Y/La/Ce elements, and plays a significant role in reducing the alloy density and improving the high-temperature performance. Specific considerations are as follows:
aluminum: the Al element is a gamma' phase forming element, and the addition of the Al can obviously reduce the alloy density due to the lower density of the Al. Too high Al element easily causes beta phase formation, so that the content of Al element is 5 to 11 at%.
Tungsten: the W element is a gamma' -phase-forming element and a solid-solution strengthening element, and W (rho ═ 19.3 g/cm)3) The density of (2) is higher, the addition of the W element can greatly increase the alloy density, so that the content of the W element is 0.01-3 at%.
Nickel: the Ni element is a gamma 'phase forming element, and the addition of the Ni element is beneficial to enlarging a gamma/gamma' two-phase region and greatly improving the structure stability of the cobalt-based high-temperature alloy, so that the content of the Ni element is 20-35 at%.
Chromium: the Cr element is an important oxidation-resistant and corrosion-resistant alloy element, and the addition of the Cr element can enable the surface of the material to form a compact chromium-rich oxide film under the service condition, so that the material is prevented from being further oxidized. The excessive Cr element causes instability of the γ/γ' two-phase structure and easily precipitates the σ phase at the grain boundary, so that the content of the Cr element is 8 to 18 at%.
Molybdenum: mo is an important solid solution strengthening element and a gamma' phase stabilizing element, and the formation of harmful TCP phase can be caused by excessively high Mo, so that the content of Mo is 1-6 at%.
Yttrium/lanthanum/cerium: the Y/La/Ce element can purify the matrix and the crystal boundary, the mechanical property and the oxidation resistance of the alloy are obviously improved, and the harmful phase can be formed by excessively adding the Y/La/Ce element to further deteriorate the performance, so that one of the Y, La and Ce elements is added, and the content is 0.01-1 at%.
Silicon: the addition of Si element can reduce the thickness of the oxide layer, promote the formation of chromium-rich oxide film and improve the oxidation resistance, and the addition of a large amount of Si element can reduce the stability of the gamma/gamma' two-phase structure of the alloy, so that the content of Si element is 0.01-1 at%.
Boron: the B element is an important grain boundary strengthening element and is localized at grain boundaries to strengthen the grain boundary strength, but the excessive B element can form excessive boride to weaken the bonding force of the grain boundaries, so the content of the B element is 0.01-1 at%.
Carbon: the element C is also an important grain boundary strengthening element, and excessive element C can cause grain boundary to form thin-film carbide and deteriorate the mechanical property, so the content of the element C is 0.01-1 at%.
Zirconium: zr is an important crystal boundary strengthening element and plays an important role in removing harmful impurities of sulfur and phosphorus, but excessive Zr can deteriorate the mechanical property, so that the content of the Zr element is 0.01-1 at%.
Hafnium: hf element is a gamma' -phase-forming element, which may also play an important role in purifying grain boundaries, but is expensive, and thus the content of Hf element is 0.01-1 at%.
Tantalum: ta element is an important gamma' phase forming element, and can effectively improve the mechanical property of the cobalt-based high-temperature alloy. The content of Ta element is 0-2 at% by comprehensively considering the factors of density, cost and the like.
Titanium: ti is an important gamma' phase forming element, and can effectively improve the mechanical property of the cobalt-based high-temperature alloy. Too high Ti element causes formation of β phase and a significant decrease in hot workability interval, deteriorating hot workability. Therefore, the content of Ti element is 0 to 4 at%.
Iron: the addition of Fe element can effectively reduce the alloy cost and density, but excessive Fe element can reduce the stability of a gamma/gamma' two-phase structure and the precipitation of a TCP phase, so that the content of the Fe element is 0-4 at%.
Niobium: nb is a gamma' phase-forming element, and the addition of Nb can reduce the density, but excessive Nb causes precipitation of TCP phase, so that the content of Nb is 0-4 at%.
(2) The raw materials of the smelting process are melted according to the melting point sequence, so that the problems of burning loss of low-melting-point metal, insufficient melting of high-melting-point elements and the like can be avoided, the defects of uneven components, serious macro segregation and the like in the cobalt-based high-temperature alloy ingot can be effectively avoided, and the accuracy and uniformity of chemical components of the ingot are improved.
(3) Compared with the similar gamma' -phase strengthening deformation cobalt-based/nickel-based high-temperature alloy reported recently, the density of the alloy is reduced by 0.2-0.5g/cm3The thermal processing region is increased by 100-150 ℃, and the stable gamma/gamma' two-phase structure is still kept after the aging of 700-900 ℃ for 1000-3000 h. Therefore, compared with the similar deformation cobalt-based high-temperature alloy, the alloy disclosed by the invention has lower density and higher stability of medium-temperature structure performance, and is an excellent deformation cobalt-based high-temperature structural material.
Description of the drawings:
FIG. 1 shows a gamma/gamma' two-phase structure of the LAMP-2 cobalt-based wrought superalloy after solution-aging treatment
FIG. 2 shows a gamma/gamma' two-phase structure of the LAMP-2 cobalt-based wrought superalloy after solution-aging treatment and 750 ℃ heat exposure for 2000 hours
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Example 1: Co-Ni-Cr-Al-W-Mo-Ti-Ta based wrought high temperature alloy
By referring to the influence rule of each element on the structure performance of the novel gamma' -phase reinforced cobalt-based high-temperature alloy, the novel Co-Ni-Cr-Al-W-Mo-Ti-Ta-based deformable high-temperature alloy is developed, and the specific components are shown in Table 1. In addition to the components in the table, two alloys, LAMP-1 and LAMP-2, also contain Y: 0.05 at%, Si: 0.2 at%, Zr: 0.06 at%, Hf: 0.1 at%.
The preparation process of the Co-Ni-Cr-Al-W-Mo-Ti-Ta-based deformation high-temperature alloy comprises the following steps:
(1) considering high-melting-point elements such as W, Mo and Ta, firstly, smelting Co-Mo-W-Ta intermediate alloy to reduce the melting point of the alloy, preventing the phenomenon of uneven melting of the high-melting-point alloy in the smelting process, and simultaneously, smelting the alloy elements with less content, such as: si, B, C, Zr, Hf, Y, etc., are added together with the master alloy to increase the homogeneity of these low elements.
(2) Simple substances of alloy elements except Al and Ti elements, including Ni, Cr and the like, are put into a crucible together with the intermediate alloy, and Al and Ti elements which are easy to oxidize are put into a hopper so as to be added in the smelting process.
(3) Smelting in a vacuum induction furnace with the vacuum degree lower than 5 × 10-2When Pa is reached, the raw material is heated by low-power electric power transmission to remove the adhering gas, and the vacuum is continuously pumped to 1 × 10-2And when Pa is needed, rapidly heating to 1600 ℃ with high power, preserving heat for 10 minutes, then reducing the temperature to 1400 ℃, preserving heat for 5 minutes, adding Al and Ti elements in a hopper, rapidly heating to 1600 ℃ immediately, preserving heat for 10 minutes, and then pouring to prepare the cobalt-based high-temperature alloy ingot.
After the alloy is subjected to air cooling solution treatment after heat preservation for 24h at 1230 ℃, and heat preservation for 8h of primary aging treatment at 900 ℃ and heat preservation for 12h of secondary aging treatment at 750 ℃, a stable gamma/gamma 'two-phase structure can be obtained, wherein the volume fraction of the gamma' phase is about 55-65% (as shown in figure 1)All the components are cubic or nearly cubic and are uniformly distributed in the gamma phase. The alloy still maintains a stable gamma/gamma' two-phase structure after being exposed for 2000 hours at 750 ℃ (shown in figure 2). Compared with the recently reported similar gamma' -phase strengthening deformation cobalt-based high-temperature alloy (CoWAlloy2), the density of the alloy is reduced by 0.2-0.5g/cm3Compared with the hard-deformation nickel-based high-temperature alloy (U720Li), the hot-working interval is increased by 110-150 ℃, the room-temperature hardness is equivalent to that of the U720Li alloy (shown in Table 2), and the alloy is an excellent deformation cobalt-based high-temperature structural material.
TABLE 1 atomic percentages and densities of the elements of Co-Ni-Cr-Al-W-Mo-Ti-Ta-based alloys
The CoWAlloy2 alloy data are from: free L P, Giese S, Schwimmer D, et al, high empperfeature properties and failure string length of novel while gamma/gamma' Co-based superalloys [ J ] Journal of Materials Research,2017:1-8 ]
TABLE 2 Room temperature hardness and Hot working intervals for Co-Ni-Cr-Al-W-Mo-Ti-Ta based alloys
The [ U720Li alloy data are from: zhou L Z, Lupinc V, Guo J T. evolution of Micromicroscopy and Mechanical Property reduction Long-Terming Aging in Udimet720Li [ J ]. Journal of Materials Science & Technology,2001,17(6):633-
Example 2: Co-Ni-Cr-Al-W-Mo-Ti-Nb based wrought high temperature alloy
By referring to the influence rule of each element on the structure property of the novel cobalt-based high-temperature alloy, the novel Co-Ni-Cr-Al-W-Mo-Nb-based deformation high-temperature alloy is developed, and the specific alloy components are shown in Table 3. In addition to the compositions in the table, the alloys 3# and 4# also contain La: 0.05 at%, Si: 0.2 at%, B: 0.04 at%, C: 0.05 at%, Zr: 0.06 at%, Hf: 0.1 at%.
The preparation process of the novel Co-Ni-Cr-Al-W-Mo-Ti-Nb based deformation high-temperature alloy comprises the following steps:
(1) considering high-melting-point elements such as W, Mo and Nb, firstly, smelting Co-Mo-W-Nb intermediate alloy, reducing the alloy melting point, preventing the phenomenon of uneven melting of the high-melting-point alloy in the smelting process, and simultaneously, smelting the alloy elements with less content, such as: si, B, C, Zr, Hf, La, etc. are added together with the master alloy to increase the homogeneity of these low content elements.
(2) Simple substances of alloy elements except Al and Ti elements, including Ni, Cr and the like, are put into a crucible together with the intermediate alloy, and Al and Ti elements which are easy to oxidize are put into a hopper so as to be added in the smelting process.
(3) Smelting in a vacuum induction furnace with the vacuum degree lower than 5 × 10-2When Pa is reached, the raw material is heated by low-power electric power transmission to remove the adhering gas, and the vacuum is continuously pumped to 1 × 10-2When Pa is needed, the temperature is quickly raised to 1550 ℃ in high power, the temperature is kept for 10 minutes, then the temperature is reduced to 1350 ℃, the temperature is kept for 5 minutes, Al and Ti elements in a hopper are added, then the temperature is quickly raised to 1550 ℃ immediately, and the temperature is kept
And pouring after 10 minutes to prepare the cobalt-based high-temperature alloy ingot.
After the alloy is subjected to air cooling solution treatment after heat preservation for 12h at 1230 ℃, and heat preservation for 4h of primary aging treatment at 900 ℃ and heat preservation for 12h of secondary aging treatment at 700 ℃, a stable gamma/gamma ' two-phase structure can be obtained, wherein the volume fraction of the gamma ' phase is about 40-50%, and the gamma ' phase is cubic or nearly cubic and is uniformly distributed in the gamma phase. After the alloy is exposed to 700 ℃ for 2000h, the stable gamma/gamma' two-phase structure is still maintained. Compared with the recently reported similar gamma' -phase strengthening deformation cobalt-based high-temperature alloy (CoWAlloy2), the density of the alloy is reduced by 0.3-0.5g/cm3Compared with the hard-deformation nickel-based high-temperature alloy (U720Li), the hot-working interval is improved by 120-140 ℃, the room-temperature hardness is equivalent to that of the U720Li alloy (shown in Table 4), and the alloy is an excellent deformation cobalt-based high-temperature structural material.
TABLE 3 atomic percentages and densities of the elements of Co-Ni-Cr-Al-W-Mo-Ti-Nb based alloys
TABLE 4 Room temperature hardness and Hot working intervals for Co-Ni-Cr-Al-W-Mo-Ti-Nb based alloys
Example 3: Co-Ni-Cr-Al-W-Mo-Ti-Fe-based wrought high temperature alloy
By referring to the influence rule of each element on the structure property of the novel cobalt-based high-temperature alloy, the novel Co-Ni-Cr-Al-W-Mo-Fe-based deformation high-temperature alloy is developed, and the specific alloy components are shown in Table 5. In addition to the ingredients in the table, the alloy also contains Ce: 0.05 at%, Si: 0.25 at%, B: 0.06 at%, C: 0.05 at%, Zr: 0.04 at%, Hf: 0.05 at%.
The preparation process of the Co-Ni-Cr-Al-W-Mo-Ti-Fe-based deformation high-temperature alloy comprises the following steps:
(1) considering W, Mo and other high-melting-point elements, firstly, smelting Co-Mo-W intermediate alloy to reduce the melting point of the alloy, preventing the phenomenon of uneven melting of the high-melting-point alloy in the smelting process, and simultaneously, smelting the alloy with less content of alloy elements, such as: si, B, C, Zr, Hf, Ce, etc., are added together with the master alloy to increase the homogeneity of these low elements.
(2) Simple substances of alloy elements except Al and Ti elements, including Ni, Cr, Fe and the like, are put into a crucible together with the intermediate alloy, and Al and Ti elements which are easy to oxidize are put into a hopper so as to be added in the smelting process.
(3) Smelting in a vacuum induction furnace with the vacuum degree lower than 5 × 10-2When Pa is reached, the raw material is heated by low-power electric power transmission to remove the adhering gas, and the vacuum is continuously pumped to 1 × 10-2And when Pa is needed, rapidly heating to 1500 ℃ at high power, preserving heat for 10 minutes, then reducing the temperature to 1300 ℃, preserving heat for 5 minutes, adding Al and Ti elements in a hopper, rapidly heating to 1500 ℃ immediately, preserving heat for 15 minutes, and then pouring to prepare the cobalt-based high-temperature alloy ingot.
After the alloy is subjected to air cooling solution treatment after heat preservation for 12h at 1220 ℃, primary aging treatment for 4h at 900 ℃ and secondary aging treatment for 12h at 700 ℃, a stable gamma/gamma ' two-phase structure can be obtained, wherein the volume fraction of the gamma ' phase is about 35-45%, the gamma ' phase is spherical or nearly cubic and is uniformly distributed in the gamma phase. After the alloy is exposed to 700 ℃ for 2000h, the stable gamma/gamma' two-phase structure is still maintained. The alloy has a density reduction of about 0.4g/cm compared to a recently reported homogeneous gamma prime phase strengthened wrought cobalt-based superalloy (CoWAlloy2)3Compared with the hard-deformation nickel-based high-temperature alloy (U720Li), the hot-working interval is improved by 120-140 ℃, the room-temperature hardness is equivalent to that of the U720Li alloy (shown in Table 6), and the alloy is an excellent deformation cobalt-based high-temperature structural material.
TABLE 5 atomic percentages and densities of the elements of Co-Ni-Cr-Al-W-Mo-Ti-Fe-based alloys
TABLE 6 Room temperature hardness and Hot working intervals for Co-Ni-Cr-Al-W-Mo-Ti-Fe-based alloys
Claims (2)
1. A cobalt-based high-temperature alloy with low density and high structure stability is characterized in that the alloy comprises the following chemical components in atomic percent: 5-11% of Al, 0.01-3% of W, 20-35% of Ni, 8-18% of Cr, 1-6% of Mo, 0.01-1% of Si, 0.01-1% of B, 0.01-1% of C, 0.01-1% of Zr, 0.01-1% of Hf, one of Y, Ce or La, 0.01-1% of Hf, 0-2% of Ta, 0-4% of Ti, 0-4% of Fe, 0-4% of Nb and the balance of Co;
the cobalt-based alloy with low density and high structure stability is a gamma '-phase reinforced cobalt-based high-temperature alloy which mainly depends on gamma' -Co which is compatible with a matrix3Strengthening by (Al, W) phase;
after the alloy is subjected to solution treatment and aging at the temperature of 700 ℃ for 1000-3000h, a stable gamma/gamma' two-phase structure is still kept;
the alloy is of the same kindCompared with the gamma' phase strengthening deformation cobalt-based high-temperature alloy, the density is reduced by 0.2 to 0.5g/cm3Compared with the hard-deformation nickel-based high-temperature alloy U720Li, the hot working range is improved by 100-150 ℃, and the room temperature hardness is equivalent to that of the U720Li alloy.
2. The method for preparing a cobalt-based superalloy with low density and high structural stability as defined in claim 1, wherein the method comprises an intermediate alloy smelting process and an alloy smelting process, and the preparation steps are as follows:
(1) firstly, smelting Co-Mo-W-Ta-Nb intermediate alloy, reducing the melting point of the alloy, and preventing the phenomenon of insufficient melting of high-melting-point alloy in the smelting process; meanwhile, alloying elements with small content, such as Si, B, C, Zr, Hf and Y/Ce/La, are added into the intermediate alloy together to increase the uniformity of the low-content elements;
(2) putting alloy elements, namely simple substances Ni, Cr and Fe except Al and Ti, and an intermediate alloy into a crucible, and putting easily oxidized Al and Ti into a hopper so as to be added in the smelting process;
(3) smelting in a vacuum induction furnace with the vacuum degree lower than 5 × 10-2When Pa is reached, the raw material is heated by low-power electric power transmission to remove the adhering gas, and the vacuum is continuously pumped to 1 × 10-2And when Pa is needed, rapidly heating to 1500-1600 ℃ with high power, preserving heat for 10 minutes, then reducing the temperature to 1300-1400 ℃, preserving heat for 5 minutes, adding Al and Ti elements in a hopper, immediately and rapidly heating to 1500-1600 ℃, preserving heat for 10-15 minutes, and then pouring to prepare the cobalt-based high-temperature alloy ingot.
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US6921586B2 (en) * | 2002-02-05 | 2005-07-26 | General Electric Company | Ni-Base superalloy having a coating system containing a diffusion barrier layer |
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