CN113265564B - High-temperature alloy with good long-term stability and preparation method thereof - Google Patents
High-temperature alloy with good long-term stability and preparation method thereof Download PDFInfo
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- CN113265564B CN113265564B CN202110492321.8A CN202110492321A CN113265564B CN 113265564 B CN113265564 B CN 113265564B CN 202110492321 A CN202110492321 A CN 202110492321A CN 113265564 B CN113265564 B CN 113265564B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
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- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
Abstract
The invention discloses a high-temperature alloy with good long-term stability, which comprises the following components in percentage by weight: c: 0.05-0.16%; cr: 8.0-9.5%; co: 9-10.5%; w: 9.0-10.5%; mo: 0.2-1.0%; ta: 2.5-3.5%; al: 5.0-6.0%; ti: 0.5-1.5%; b: 0.01-0.02%; hf: 1.0-2.0%; zr: 0.004-0.06%; mg: 0.001-0.005%; si is less than or equal to 0.15 percent; mn is less than or equal to 0.05 percent; the balance being Ni and unavoidable impurities by mass; wherein the B, Mg mass percentage content satisfies the relation that B +12.6Mg is more than or equal to 0.032% and less than or equal to 0.068%. The high-temperature alloy with good long-term stability has excellent mechanical property, long-term stability and long service life, completely meets the design and use requirements of advanced aeroengines and gas turbines, and is suitable for parts in service for medium and long periods, such as turbine blades of hot-end parts of aeroengines and gas turbines.
Description
Technical Field
The invention belongs to the technical field of high-temperature alloys, particularly relates to a high-temperature alloy with good long-term stability, and particularly relates to a preparation method of the high-temperature alloy with good long-term stability.
Background
The requirements of the prior advanced aeroengine and gas turbine on the initial processing precision and the assembly precision of a precise hot end part are extremely high, and failure fracture cannot occur in the high-temperature long-term service process of 800-. At present, almost no alloy which can completely meet the requirements exists in the existing high-temperature alloys at home and abroad, the long-term stability of the alloy which can generally achieve the mechanical properties is poor, and a TCP phase is separated out after 2000 hours of treatment, so that the properties are reduced.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: the high-temperature alloy used in the fields of advanced aeroengines, gas turbines and the like at present can not meet the requirements, and the required high-temperature alloy has the following requirements on specific performance indexes: the tensile property Rm at room temperature is more than or equal to 966MPa, Rp0.2 is more than or equal to 725MPa, and A is more than or equal to 6 percent; rm is more than or equal to 700MPa at the high-temperature stretching temperature of 900 ℃, Rp0.2 is more than or equal to 420MPa, A is more than or equal to 6 percent, and the lasting time is more than 65 hours at 980 ℃ and 200 MPa; TCP phase can not be precipitated after the treatment for 3000 hours at 950 ℃, but no high-temperature alloy can meet the requirements at present.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the high-temperature alloy with good long-term stability and the preparation method thereof are provided by the embodiment of the invention, the high-temperature alloy with good long-term stability not only has excellent mechanical properties, but also has long-term stability and long service life, completely meets the requirements of design and use of advanced aeroengines and gas turbines, and is suitable for parts in medium-and long-term service such as turbine blades of hot-end parts of aeroengines and gas turbines.
The high-temperature alloy with good long-term stability according to the embodiment of the invention comprises the following components: b is more than or equal to 0.032 percent and less than or equal to 0.068 percent of Mg, and the balance is Ni and inevitable impurities by mass;
wherein the B, Mg mass percentage content satisfies the relation that B +12.6Mg is more than or equal to 0.032% and less than or equal to 0.068%.
According to the advantages and technical effects brought by the high-temperature alloy with good long-term stability in the embodiment of the invention, 1, the design scheme of high-Al, low-Ti and high-Ta strengthening elements is adopted in the embodiment of the invention, and the traditional Ni is subjected to Ni-based alloy3The (Al, Ti) strengthening phase is modified to form Ni containing higher Al content and Ta3(Al, Ti, Ta) strengthening phase, compared with the traditional Ni3The high-temperature alloy in the embodiment of the invention has more excellent high-temperature resistance; 2. the alloy of the embodiment of the invention limits the mass percentage of the element B, Mg to meet the relation that B +12.6Mg is more than or equal to 0.032% and less than or equal to 0.068%, so that the alloy has excellent tensile property and long service life, and the alloy does not precipitate TCP phase after being treated for 3000 hours at 950 ℃, and has excellent long-term service stability, therefore, the alloy of the embodiment of the invention can meet the design and use requirements of advanced aeroengines and gas turbines.
According to the high-temperature alloy with good long-term stability, the mass percentage of Al, Ti and Ta satisfies the relation that Al + Ti + Ta is more than or equal to 9.1% and less than or equal to 9.9%.
The preparation method of the high-temperature alloy with good long-term stability, provided by the embodiment of the invention, comprises the following steps:
a. adding Cr, Co, W, Mo, Ta, B, Hf, Zr, Mg, Si, Mn and part of C raw materials into a crucible according to the required alloy proportion, heating the crucible under a vacuum condition to melt the raw materials in the crucible, and then preserving heat;
b. stopping heating the crucible, naturally cooling, introducing argon into the crucible, adding Al, Ti and the rest C raw materials into the crucible, vacuumizing to melt the raw materials in the crucible, and casting to obtain the high-temperature alloy.
According to the advantages and the technical effects brought by the preparation method of the high-temperature alloy with good long-term stability, 1, in the embodiment of the invention, the C element in the nickel-based high-temperature alloy belongs to an element easy to burn and damage, so the C element is added step by step and in different proportions, part of C is added for the first time, the refining temperature is higher in the initial smelting period, the alloying material is faster, and the C element reacts with O in the raw material in the crucible to generate CO2And the gas overflows to facilitate the removal of the gas in the alloy. The residual C is added for the second time, so that the content of C in the alloy can be effectively controlled, and the mechanical property of the alloy is improved; 2. according to the method provided by the embodiment of the invention, the raw materials with specific element proportions are adopted, so that the prepared alloy has excellent tensile property and long service life, a TCP phase is not precipitated after the alloy is treated at 950 ℃ for 3000 hours, the alloy has excellent long-term service stability, and the design and use requirements of advanced aeroengines and gas turbines can be met.
According to the preparation method of the high-temperature alloy with good long-term stability, disclosed by the embodiment of the invention, part of the raw material C added in the step a is 10-20% of the designed consumption of the raw material C.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step a, the vacuum condition is that the vacuum degree is less than 0.1 Pa.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step a, the heat preservation temperature is 1600-1650 ℃, and/or the heat preservation time is 10-30 min.
According to the preparation method of the high-temperature alloy with good long-term stability, disclosed by the embodiment of the invention, in the step b, the natural cooling temperature is 1200-1400 ℃.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, argon is introduced into the crucible until the pressure in the crucible is-0.02 MPa to-0.1 MPa.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, the vacuum degree in the crucible is less than 0.1Pa after the vacuum pumping.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, the casting temperature is more than or equal to 1560 ℃.
Drawings
FIG. 1 is an SEM image of the alloy obtained in example 1 after treatment at 950 ℃ for 3000 hours;
FIG. 2 is an SEM image of the alloy obtained in comparative example 1 after treatment at 950 ℃ for 3000 hours.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The high-temperature alloy with good long-term stability according to the embodiment of the invention comprises the following components: c: 0.05-0.16%; cr: 8.0-9.5%; co: 9-10.5%; w: 9.0-10.5%; mo: 0.2-1.0%; ta: 2.5-3.5%; al: 5.0-6.0%; ti: 0.5-1.5%; b: 0.01-0.02%; hf: 1.0-2.0%; zr: 0.004-0.06%; mg: 0.001-0.005%; si is less than or equal to 0.15 percent; mn is less than or equal to 0.05 percent; the balance being Ni and unavoidable impurities by mass;
wherein the B, Mg mass percentage content satisfies the relation that B +12.6Mg is more than or equal to 0.032% and less than or equal to 0.068%.
According to the advantages and technical effects brought by the high-temperature alloy with good long-term stability, the embodiment of the invention adopts a design scheme of high-Al, low-Ti and high-Ta strengthening elements to the traditional Ni3The (Al, Ti) strengthening phase is modified to form Ni containing higher Al content and Ta3(Al, Ti, Ta) strengthening phase, compared with the traditional methodNi of (2)3The high-temperature alloy in the embodiment of the invention has more excellent high-temperature resistance; the alloy of the embodiment of the invention limits the mass percentage of the element B, Mg to meet the relation that B +12.6Mg is more than or equal to 0.032% and less than or equal to 0.068%, so that the alloy has excellent tensile property and long service life, the tensile property Rm at room temperature is more than or equal to 966MPa, Rp0.2 is more than or equal to 725MPa, and A is more than or equal to 6%; rm is more than or equal to 700MPa at the high-temperature stretching temperature of 900 ℃, Rp0.2 is more than or equal to 420MPa, A is more than or equal to 6 percent, and the lasting time is more than 65 hours at 980 ℃ and 200 MPa; the alloy does not precipitate TCP phase after being treated for 3000 hours at 950 ℃, and has excellent long-term service stability. Can meet the requirements of the design and the use of advanced aeroengines and gas turbines.
The alloy of the embodiment of the invention has the following main elements:
c: c in Ni-based superalloy inhibits austenite grain growth during heating mainly by forming MC type carbide at the final stage of solidification and forms M along grain boundary during heat treatment23C6The carbides of the same type play a role in strengthening the grain boundary and can delay the initiation, the expansion and the combination of microcracks, thereby improving the high-temperature durable life of the alloy, and when the content of C is less than 0.05 percent, the sufficient amount of MC and M cannot be formed23C6. When the content of C is too high, the formed MC is large in size and excessively consumes Mo, Cr, Ti and Ta in the alloy, so that the solid solution strengthening effect of the Mo and the Cr is reduced, and the formed MC is used for forming Ni3(Al, Ti) and Ni3Ti and Ta of the (Al, Ti and Ta) composite strengthening phase are reduced, and the high-temperature performance and the durability of the alloy are adversely affected, so that C is controlled to be not more than 0.16%.
Cr: cr has the main function of improving the oxidation resistance of the alloy, has certain solid solution strengthening effect, and can be combined with C to form granular M distributed along the crystal after aging treatment23C6And the function of strengthening the grain boundary is achieved. However, when the content of Cr is too high, a TCP phase is easily formed, and the stability of the long-term structure performance of the alloy is reduced, so that the content of Cr is generally not more than 25%.
Co: co is an important solid-solution strengthening element and also an important precipitation strengthening element. Co element can be dissolved in the matrix in a solid manner to provide good solid solution strengthening effect for the alloy, can obviously reduce the stacking fault energy of the matrix, widen and expand the dislocation width, and ensure that dislocation is not easy to bunch and generate cross slip, thereby improving the creep resistance and the endurance life of the alloy. Co may also partially replace Ni3The Al-type phase precipitates elements in a strengthening phase, so that the stability of the phase in long-term service is improved; co can also reduce the solid solubility of Al and Ti elements in a matrix, promote the precipitation of a gamma' strengthening phase and improve the precipitation quantity and the solid solution temperature. When the Co content is lower than 9%, the high-temperature strength is low, and when the Co content is higher than 11%, eta phase influencing the performance of the product is easily formed in long-term service, so that the Co content is controlled to be 9.0-10.5%.
W and Mo: w and Mo are one of main solid solution strengthening elements, can be dissolved in an alloy matrix in a solid mode and can be dissolved in a gamma' strengthening phase in a solid mode, and meanwhile, the interatomic binding force can be improved, the diffusion activation energy and the recrystallization temperature can be improved, so that the high-temperature strength can be effectively improved. However, when Mo is too high, the long-term high-temperature aging is easy to generate a mu phase, thereby reducing the toughness of the alloy. Therefore, the Mo content is controlled to 0.2 to 1.0%. The radius of W atom is bigger than that of Ni atom by more than ten percent, and the solid solution strengthening effect is obvious. However, W is an element for accelerating high-temperature corrosion, and a harmful delta phase is formed in long-term service, so that the strength and the toughness of the alloy are reduced. Therefore, the W content is controlled to be 9.8-10.5%.
Al, Ti and Ta: the three elements are forming elements of a strengthening phase gamma ' in the nickel-based alloy, and generally, the number of the gamma ' is increased along with the increase of the contents of the three elements, the high-temperature creep and the endurance performance are improved, but the processability is deteriorated by the excessive gamma '. In addition, Ti and Ta combine with C to form MC type carbide, which inhibits grain boundary growth and grain boundary sliding at high temperature and plays a role in improving high temperature mechanical properties, but too much Ti and Ta forms large-particle MC type carbide, which is disadvantageous to mechanical properties of the alloy. The invention discovers through research that the high-temperature mechanical property of the alloy not only depends on the amount of the gamma 'phase, but also depends on the composition and the characteristics of the gamma' phase, and the high-temperature mechanical property of the alloy can be optimized through the proportion of Al, Ti and Ta on the premise that the total amount of Al, Ti and Ta is not changedThe best gamma prime strengthening effect is obtained. The alloy of the embodiment of the invention adopts a design scheme of high Al, low Ti and high Ta strengthening elements to the traditional Ni3The (Al, Ti) strengthening phase is modified to form Ni containing higher Al content and Ta3(Al, Ti, Ta) more conventional than Ni3The (Al and Ti) strengthening phase is more resistant to high temperature, thereby improving the tensile property and the endurance life of the alloy. The specific control ranges of the three are as follows: al: 5.0-6.0%, Ti: 0.5-1.5%, Ta: 2.5 to 3.5 percent.
B: the function of B is mainly shown in two aspects, firstly, because the atomic radius of B is very small and is only about 85 picometers, and the radius of Ni atomic is about 135 picometers, B atoms are easy to be enriched in grain boundaries, so that harmful low-melting-point elements cannot be segregated in the grain boundaries, and the bonding force of the grain boundaries is improved; secondly, boride on the grain boundary can prevent grain boundary sliding and cavity initiation and expansion, and is beneficial to improving the creep resistance and the endurance life of the alloy. However, too much B deteriorates the hot workability and weldability of the alloy, so that the alloy of the embodiment of the present invention is preferably selected to have a B content of 0.01 to 0.02%.
Zr: zr is beneficial to purifying grain boundaries and enhancing grain boundary binding force, the composite addition of Zr and B is beneficial to maintaining the high-temperature strength and the long-lasting life of the alloy, but excessive Zr is easy to reduce the processing performance, and the Zr is controlled to be 0.004-0.06% by the alloy in the embodiment of the invention.
Mg: the high-temperature alloy is microalloyed by Mg, Mg atoms are partialized on a grain boundary, and the partialization belongs to equilibrium partialization. Mg is segregated in the grain boundary to improve the bonding force of the grain boundary and increase the strength of the grain boundary. The Mg atoms are not only localized to the grain boundaries but also to the carbide phase boundary, the γ' phase boundary. Mg atoms also enter γ' and carbides, thus having a favorable effect on mechanical properties. The trace Mg is segregated in the grain boundary to reduce the grain boundary energy and the phase boundary energy and improve and refine the forms of grain boundary carbide-grade other grain boundary precipitated phases. For example, the carbide is made into a lump or spheroidized, thereby effectively suppressing the sliding of grain boundaries, reducing the stress concentration of grain boundaries, and eliminating the notch sensitivity. Mg and harmful impurities such as sulfur form high-melting-point compounds such as MgS, etc., purify grain boundaries, obviously reduce the concentration of impurity elements such as S, O, P, etc. in the grain boundaries, and reduce the harmful effects of impurities such as S, O, P, etcThe application is as follows. The trace Mg improves the endurance time and plasticity, improves the creep property and the high-temperature tensile plasticity, increases the impact toughness and the fatigue strength, and can also improve the hot working performance and the yield for some alloys. However, the content is not too high, and too high deteriorates the properties, and Ni-Ni, for example, may be formed2Mg eutectic with a low melting point (1050 ℃ C.), deteriorates the hot workability. Similarly, too low a content does not fully exert its advantageous effects. Therefore, the Mg content is controlled to be 0.001 to 0.005%.
According to the high-temperature alloy with good long-term stability, the mass percentage of Al, Ti and Ta satisfies the relation that Al + Ti + Ta is more than or equal to 9.1% and less than or equal to 9.9%. In the embodiment of the invention, a design scheme of high Al, low Ti and high Ta strengthening elements is adopted for the traditional Ni3The (Al, Ti) strengthening phase is modified to form Ni containing higher Al content and Ta3(Al, Ti, Ta) strengthening phase, compared with the traditional Ni3The high-temperature alloy in the embodiment of the invention has better high-temperature resistance.
The mass percentage of the elements Al, Ti and Ta in the alloy of the embodiment of the invention is limited to be more than or equal to 9.1% and less than or equal to 9.9% of the relation, and the lasting time of the alloy can be further improved by regulating and controlling the Al, Ti and Ta, so that the alloy has more excellent tensile property and lasting life.
In the embodiment of the invention, the density of the high-temperature alloy is less than or equal to 8.25g/cm3. Wherein the high temperature alloy has excellent tensile property and long service life, and the density is not more than 8.25g/cm3Therefore, the alloy has light dead weight, is beneficial to reducing fuel consumption of an aeroengine and improving the maneuvering performance, and can meet the requirement that the vibration of the gas turbine is as small as possible in the working process and prevent the formation of vibration damage.
The preparation method of the high-temperature alloy with good long-term stability, provided by the embodiment of the invention, comprises the following steps:
a. adding Cr, Co, W, Mo, Ta, B, Hf, Zr, Mg, Si, Mn and part of C raw materials into a crucible according to the required alloy proportion, heating the crucible under a vacuum condition to melt the raw materials in the crucible, and then preserving heat;
b. stopping heating the crucible, naturally cooling, introducing argon into the crucible, adding Al, Ti and the rest C raw materials into the crucible, vacuumizing to melt the raw materials in the crucible, and casting to obtain the high-temperature alloy.
According to the advantages and technical effects brought by the preparation method of the high-temperature alloy with good long-term stability, 1, in the embodiment of the invention, the element C in the nickel-based high-temperature alloy belongs to elements easy to burn and damage. Therefore, the C element is added step by step according to different proportions, part of the C is added for the first time, the refining temperature is higher in the initial smelting stage, the alloying material is quicker, and the C element reacts with O in the raw material in the crucible to generate CO2And the gas overflows to facilitate the removal of the gas in the alloy. The residual C is added for the second time, so that the content of C in the alloy can be effectively controlled, and the mechanical property of the alloy is improved; 2. according to the method provided by the embodiment of the invention, the raw materials with specific element proportions are adopted, so that the prepared alloy has excellent tensile property and long service life, a TCP phase is not precipitated after the alloy is treated at 950 ℃ for 3000 hours, the alloy has excellent long-term service stability, and the design and use requirements of advanced aeroengines and gas turbines can be met.
In the embodiment of the invention, the raw materials of each component in the high-temperature alloy are as follows:
cr is at least one of ferrochrome, metal chromium, brocade ferrochrome, low-nitrogen brocade ferrochrome and high-purity low-oxygen chromium;
co is at least one of electrolytic cobalt, metallic cobalt and a Jinchuan cobalt plate;
w is at least one of ferrotungsten, a tungsten rod and a high-purity tungsten block;
mo is at least one of metal molybdenum, ferromolybdenum and molybdenum chromium rods;
ta is at least one of metal Ta and smelting Ta;
al is at least one of electrolytic aluminum, aluminum bar and pure aluminum strip;
ti is at least one of pure titanium rod, metallic titanium and titanium sponge;
b is ferroboron;
hf is at least one of metal hafnium and high-purity hafnium rod;
zr is sponge zirconium; ni is at least one of electrolytic nickel, metallic nickel, gold nickel and high-purity nickel;
si is at least one of high-carbon silicon, high-carbon ferrosilicon, high-purity polycrystalline silicon and metal silicon particles;
mn is at least one of ferromanganese, metal manganese and electrolytic manganese sheets.
According to the preparation method of the high-temperature alloy with good long-term stability, disclosed by the embodiment of the invention, part of the raw material C added in the step a is 10-20% of the designed consumption of the raw material C. According to the preparation method of the high-temperature alloy with good long-term stability, in the step a, the vacuum condition is that the vacuum degree is less than 0.1 Pa. In the embodiment of the invention, the vacuum degree in the crucible needs to be controlled when alloying materials. Under a higher vacuum degree, the alloy is heated and vacuumized at the same time, so that the overflow of gas in the alloy is facilitated, the reaction of C and O in the alloy is accelerated, and the purity of the alloy is improved.
In the embodiment of the invention, the heating time of the crucible in the step a is 15-30 min. In the embodiment of the invention, the alloy is rapidly heated and rapidly smelted under a higher vacuum degree, so that the energy consumption can be reduced, and on the other hand, the raw materials in the crucible are rapidly melted to form a liquid-phase molten pool so as to provide the reaction condition of C and O.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step a, the heat preservation temperature is 1600-1650 ℃, and/or the heat preservation time is 10-30 min. In the embodiment of the invention, in the high-temperature alloy refining period, heat preservation measures are adopted, so that on one hand, all elements of the alloy can be uniformly mixed, and on the other hand, gas in the alloy can be fully removed at the heat preservation temperature.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, the natural cooling time is 5-15min, and the natural cooling temperature is 1200-1400 ℃. In the embodiment of the invention, C, Al and Ti are elements easy to burn and damage, and are easy to react with gas to cause deviation of alloy elements. Therefore, the temperature of the alloy liquid in the crucible needs to be reduced to 1200-1400 ℃, so that the alloy liquid is ensured to be in a liquid state, and the temperature interval of the maximum burning loss can be avoided.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, argon is introduced into the crucible until the pressure in the crucible is-0.02 MPa to-0.1 MPa. In the embodiment of the invention, after the C, Al and Ti raw materials are added, O in the alloy liquid reacts with the elements rapidly, the reaction cannot be completely inhibited even if the temperature is controlled, and the liquid level of the liquid alloy liquid violently surges along with the reaction in the reaction process.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, after the liquid alloy is calm, vacuum pumping is carried out, so that the vacuum degree in the crucible is less than 0.1 Pa. In the embodiment of the invention, after argon is introduced, the overflow of gas in the alloy is effectively inhibited, the splashing of alloy liquid is prevented, and after the C, Al and Ti raw material alloy liquid is added and calmed, the gas in the alloy liquid is extracted by adopting vacuum-pumping treatment, so that the purity of the alloy is improved.
According to the preparation method of the high-temperature alloy with good long-term stability, in the step b, the temperature of the crucible in the step c is adjusted to be not less than 1560 ℃, the crucible is cast into a mold, and after the crucible is naturally cooled to the room temperature, the mold is demolded to carry out surface sand blasting polishing and remove oxide skin, so that the high-temperature alloy is obtained. In the embodiment of the invention, if the alloy discharging temperature is lower than 1560 ℃, the fluidity of the alloy liquid is poor, and the alloy liquid is not beneficial to flowing in the alloy discharging process. This results in the alloy liquid being poured into the mold at too low a temperature and even beginning to solidify, in which case the alloy liquid is liable to crack when cooled in the mold and break when demolded.
The present invention will be described in detail with reference to examples.
Example 1
The alloy comprises the following components in percentage by weight: 0.11 percent; cr: 8.7 percent; co: 9.7 percent; w: 9.8 percent; mo: 0.6 percent; ta: 3.1 percent; al: 5.6 percent; ti: 0.8 percent; b: 0.016 percent; hf: 1.5 percent; zr: 0.03 percent; mg: 0.003%; si: 0.01 percent; mn: 0.01 percent; the balance being Ni and unavoidable impurities. Proportioning according to the mass percent of the chemical components of the alloy, wherein Cr is metallic chromium; co is electrolytic cobalt; w is a tungsten rod; mo is metal molybdenum; ta is metal Ta; al is electrolytic aluminum or aluminum bar; ti is a pure titanium rod; b is ferroboron; hf is metal hafnium; zr is sponge zirconium; ni is electrolytic nickel; si is high carbon silicon; mn is metal manganese.
Mixing C, Cr and Ni raw materials, putting the mixture into the bottom of a crucible, and proportionally filling Mo and Ta on the upper part of the crucible. The other raw materials are placed in layers. Vacuumizing, heating within 15min to completely melt, controlling the temperature at 1600 deg.C, maintaining the vacuum degree at less than 0.1Pa for 10min, stopping heating, maintaining for 5min, and adding C, Al and Ti; and (3) filling argon into the furnace to-0.02 MPa while adding, and vacuumizing the alloy liquid after the alloy liquid is calm, wherein the vacuum degree is less than 0.1 Pa. Adjusting the temperature to 1560 ℃, taking out the alloy, casting, cooling to room temperature, demoulding, and carrying out surface sand blasting and coping to remove oxide skin.
As shown in FIG. 1, which is an SEM image of the alloy prepared in example 1 after being treated at 950 ℃ for 3000 hours, it can be seen from FIG. 1 that after the alloy is treated for 3000 hours, the reinforcing phase gamma 'phase boundary in the structure is clear, the gamma' phase is uniform, and no significant aggregation occurs. Meanwhile, no harmful phase of TCP is separated out.
The superalloy prepared according to the method of this example B +12.6Mg =0.0538, Al + Ti + Ta =9.5%, and the alloy density was 8.17g/cm3The material has excellent tensile property and long service life, and the tensile property Rm 1025MPa, Rp0.2849MPa and A6.5 percent at room temperature; stretching at the high temperature of 900 ℃ Rm 802MPa, Rp0.245MPa, A6.5 percent, 980 ℃ and lasting time of 110h under 200 MPa; and after being treated at 950 ℃ for 3000 hours, a TCP phase is not precipitated, so that the high-temperature-resistant high-temperature-pressure-resistant high-temperature-resistant high-performance liquid crystal has excellent long service stability and can meet the design and use requirements of advanced aeroengines and gas turbines.
Example 2
The alloy comprises the following components in percentage by weight: 0.16 percent; cr: 8.1 percent; co: 10.5 percent; w: 10.2 percent; mo: 0.8 percent; ta: 2.8 percent; al: 5.9 percent; ti: 1.2 percent; b: 0.015 percent; hf: 1.8 percent; zr: 0.06 percent; mg: 0.002%; si: 0.02 percent; mn: 0.01 percent; the balance being Ni and unavoidable impurities. Preparing the materials according to the mass percent of the chemical components of the alloy, wherein the Cr is high-purity low-oxygen chromium; co is a cobalt plate; w is ferrotungsten and a tungsten rod; mo is metal molybdenum and ferromolybdenum; ta is smelting Ta; al is electrolytic aluminum and aluminum bar; ti is a pure titanium rod; b is ferroboron; hf is metal hafnium and high-purity hafnium rod; zr is sponge zirconium; ni is electrolytic nickel and metallic nickel; si is high-carbon silicon and high-carbon ferrosilicon; mn is ferromanganese, metal manganese and electrolytic manganese sheets; mixing C, Cr and Ni raw materials, putting the mixture into the bottom of a crucible, and proportionally filling Mo and Ta on the upper part of the crucible. The other raw materials are placed in layers. Vacuumizing and heating to completely melt within 30min, controlling the temperature at 1650 ℃, controlling the vacuum degree at less than 0.1Pa, keeping for 30min, stopping heating, keeping for 15min, and adding C, Al and Ti; and (3) filling argon into the furnace to-0.1 MPa while adding, and vacuumizing the alloy liquid after the alloy liquid is calm, wherein the vacuum degree is less than 0.1 Pa. Adjusting the temperature to 1570 ℃, taking out the alloy, casting, cooling to room temperature, demoulding, and carrying out surface sand blasting and coping to remove oxide skin.
Superalloy prepared according to this example B +12.6Mg =0.0402%, Al + Ti + Ta =9.9%, alloy density 8.11g/cm3The alloy has excellent tensile property and long service life, wherein the tensile property Rm at room temperature is 995MPa, Rp 0.2839MPa and A is 7.5 percent; high-temperature stretching is carried out at 900 ℃ Rm 810MPa, Rp0.245MPa, A7.0 percent, the lasting time is 102h at 980 ℃ and 200 MPa; no TCP phase is separated out after the treatment for 3000 hours at 950 ℃, and the long-term service stability is excellent. Can meet the requirements of the design and the use of advanced aeroengines and gas turbines.
Example 3
The alloy comprises the following components in percentage by weight: 0.08 percent; cr: 9.5 percent; co: 9 percent; w: 9.3 percent; mo: 0.4 percent; ta: 3.4 percent; al: 5.1 percent; ti: 0.6 percent; b: 0.019%; hf: 1.1 percent; zr: 0.01 percent; mg: 0.002%; si: 0.009%; mn: 0.02 percent; the balance being Ni and unavoidable impurities. Mixing the components according to the mass percentage of the chemical components of the alloy, wherein Cr is ferrochrome, metal chromium and low-nitrogen brocade ferrochrome; co is one or more of electrolytic cobalt and a Jinchuan cobalt plate; w is one or more of ferrotungsten, a tungsten rod and a high-purity tungsten block; mo is metal molybdenum, ferromolybdenum or molybdenum-chromium rod; ta is metal Ta and smelting Ta; al is electrolytic aluminum and pure aluminum strips; ti is pure titanium rod, metal titanium and sponge titanium; b is ferroboron; hf is metal hafnium and high-purity hafnium rod; zr is sponge zirconium; ni is electrolytic nickel, metallic nickel and high-purity nickel; si is high-carbon ferrosilicon, high-purity polycrystalline silicon and metal silicon particles; mn is ferromanganese, metal manganese and electrolytic manganese sheets; C. mixing Cr and Ni raw materials, putting the mixture into the bottom of a crucible, and proportionally filling Mo and Ta on the upper part of the crucible. The other raw materials are placed in layers. Vacuumizing, heating within 25min to completely melt, controlling the temperature at 1640 deg.C, maintaining the vacuum degree at less than 0.1Pa for 27min, stopping heating, maintaining for 10min, and adding C, Al and Ti; and (3) filling argon into the furnace to-0.07 MPa while adding, and vacuumizing the alloy liquid after the alloy liquid is calm, wherein the vacuum degree is less than 0.1 Pa. Adjusting the temperature to 1580 ℃, taking out the alloy, casting, cooling to room temperature, demoulding, and performing surface sand blasting and coping to remove oxide skin.
Superalloy prepared according to this example B +12.6Mg =0.0442%, Al + Ti + Ta =9.1%, alloy density 8.25g/cm3The alloy has excellent tensile property and long service life, and the tensile property Rm 975MPa, Rp 0.2739MPa and A7 percent at room temperature; high-temperature stretching is carried out at 900 ℃ Rm 730MPa, Rp 0.2435MPa, A6.5 percent, and the lasting time is 72h at 980 ℃ and 200 MPa; no TCP phase is separated out after the treatment for 3000 hours at 950 ℃, and the long-term service stability is excellent. Can meet the requirements of the design and the use of advanced aeroengines and gas turbines.
Examples 4 to 8
The methods of examples 4-8 are the same as example 1, except that the alloy compositions, the alloy compositions of examples 4-8 are shown in Table 1, and the performance data are shown in Table 2.
TABLE 1
TABLE 2
Comparative example 1
The same as example 1, except that B, Mg% was different in the alloy, wherein B: 0.01 percent; mg: 0.001%, B +12.6Mg = 0.0226%.
The alloy properties obtained in comparative example 1 are shown in Table 3
As shown in FIG. 2, which is an SEM image of the alloy prepared in comparative example 1 after being treated at 950 ℃ for 3000 hours, it can be seen from FIG. 2 that elongated TCP phases are precipitated in the alloy structure after 3000 hours of treatment, and the number of the TCP phases is dense. The microcracks tend to grow and propagate there after the alloy is stressed and eventually lead to alloy failure.
Comparative example 2
The same as example 1, except that B, Mg% was different in the alloy, wherein B: 0.02 percent; mg: 0.005%, B +12.6Mg = 0.083%.
The alloy properties obtained in comparative example 2 are shown in Table 3
Comparative example 3
The same as in example 1, except that Ta was not contained in the alloy.
The alloy properties obtained in comparative example 3 are shown in Table 3.
TABLE 3
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The high-temperature alloy with good long-term stability is characterized by comprising the following components: c: 0.05-0.16%; cr: 8.0-9.5%; co: 9-10.5%; w: 9.0-10.5%; mo: 0.2-1.0%; ta: 2.5-3.5%; al: 5.0-6.0%; ti: 0.5-1.5%; b: 0.01-0.02%; hf: 1.0-2.0%; zr: 0.004-0.06%; mg: 0.001-0.005%; si is less than or equal to 0.15 percent; mn is less than or equal to 0.05 percent; the balance being Ni and unavoidable impurities by mass;
wherein the mass percentage of B, Mg satisfies the relation that B +12.6Mg is more than or equal to 0.0392% and less than or equal to 0.068%.
2. The superalloy with good long-term stability according to claim 1, wherein the mass percentage of Al, Ti, and Ta satisfies the relationship of 9.1% or more and 9.9% or less with respect to Al + Ti + Ta.
3. A method for preparing a high temperature alloy with good long term stability according to any one of claims 1 or 2, which comprises the following steps:
a. according to the design proportion of alloy, adding Cr, Co, W, Mo, Ta, B, Hf, Zr, Mg, Si, Mn and part of C raw materials into a crucible, heating the crucible under a vacuum condition to melt the raw materials in the crucible, and preserving heat;
b. stopping heating the crucible, naturally cooling, introducing argon into the crucible, adding Al, Ti and the rest C raw materials into the crucible, vacuumizing to melt the raw materials in the crucible, and casting to obtain the high-temperature alloy.
4. The method for preparing a high-temperature alloy with good long-term stability as claimed in claim 3, wherein the part of the raw material C added in the step a is 10-20% of the designed amount of the raw material C.
5. The method of claim 3, wherein in step a, the vacuum condition is a degree of vacuum < 0.1 Pa.
6. The method for preparing the high-temperature alloy with good long-term stability according to claim 3, wherein in the step a, the heat preservation temperature is 1600-1650 ℃, and the heat preservation time is 10-30 min.
7. The method for preparing a high-temperature alloy with good long-term stability according to claim 3, wherein in the step b, the natural cooling temperature is 1200-1400 ℃.
8. The method for preparing a high-temperature alloy with good long-term stability according to claim 3, wherein in the step b, argon is introduced into the crucible until the pressure in the crucible is-0.02 to-0.1 MPa.
9. The method according to claim 3, wherein in the step b, the degree of vacuum in the crucible is less than 0.1Pa after the evacuation.
10. The method for preparing high-temperature alloy with good long-term stability according to claim 3, wherein in the step b, the casting temperature is not less than 1560 ℃.
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| CN105506387B (en) * | 2015-12-21 | 2017-08-08 | 谷月恒 | A kind of nickel-base high-temperature single crystal alloy of high specific creep intensity and its preparation method and application |
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