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CN114453567A - High-temperature alloy solidification structure refiner and preparation method and application thereof - Google Patents

High-temperature alloy solidification structure refiner and preparation method and application thereof Download PDF

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Publication number
CN114453567A
CN114453567A CN202210098759.2A CN202210098759A CN114453567A CN 114453567 A CN114453567 A CN 114453567A CN 202210098759 A CN202210098759 A CN 202210098759A CN 114453567 A CN114453567 A CN 114453567A
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refiner
temperature alloy
powder
solidification structure
superalloy
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CN114453567B (en
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吴继礼
倪超
梁向锋
汪存龙
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Jiangsu University
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Jiangsu University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00Treatment of fused masses in the ladle or the supply runners before casting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B22D27/045Directionally solidified castings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • C22C1/1047Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention provides a high-temperature alloy solidification structure refiner, a preparation method and application thereof, belonging to the technical field of high-temperature alloy casting; in the invention, powder with a size less than 25 microns is screened out as a refiner by ball milling powder mixing, calcining and further ball milling mechanical alloying; the refiner can be added when the high-temperature alloy liquid is above the melting point of the high-temperature alloy liquid and is stirred and mixed by adopting electromagnetism; the solidification structure of the high-temperature alloy casting or ingot can be refined efficiently, and the uniformity of the solidification structure of the high-temperature alloy is improved; and the refiner is added into the high-temperature alloy melt without bringing any harmful elements or impurities.

Description

High-temperature alloy solidification structure refiner and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high-temperature alloy casting, and particularly relates to a high-temperature alloy solidification structure refiner, and a preparation method and application thereof.
Background
The high-temperature alloy is widely applied to manufacturing of core hot end parts of aircraft engines and gas turbines due to excellent comprehensive mechanical property, creep resistance, fatigue resistance and corrosion resistance. The cast superalloy can produce near net shape or zero-allowance aircraft gas turbine engine turbine blades, guide vanes, or cast block turbines and vanes, augmentors, turbine casings, and jet nozzle vanes, among others, having complex structures and shapes. However, due to the sequential solidification characteristics of the superalloy, solidification defects such as segregation, shrinkage cavities, cracks and the like are generated in the casting or ingot structure, the service performance of the superalloy is greatly damaged, and the defects are difficult to eliminate through subsequent heat treatment or plastic working.
At present, the equiaxial crystal proportion is improved and equiaxial crystal grains are refined by improving the uniformity of a solidification structure of the high-temperature alloy, so that the solidification defect is eliminated, and the plastic processing and service performance of the high-temperature alloy are improved. The method adopts a refiner to refine the high-temperature alloy solidification structure, and the basic principle is that a large amount of effective nucleation mass points are introduced into a high-temperature alloy melt and can be used as heterogeneous nucleation cores in the subsequent solidification process, so that the nucleation rate is improved, the purpose of refining grains is achieved, and the performance of a casting is improved. In the selection of the refiner, certain crystallographic and melt-matching requirements are often followed, i.e. the degree of lattice mismatch between the refiner and the solidification matrix grains is less than 9% and the smaller the better. Furthermore, it is also desirable to comply with the introduction of no harmful impurities or inclusions into the superalloy melt. In addition, in order to ensure the structural uniformity of the casting or ingot, the stability of the refiner in the high-temperature melt and the density close to that of the high-temperature alloy melt are also considered. The commonly used high-temperature alloy refiner mainly comprises intermetallic compounds, metal oxides, nitrides, carbides and the like which follow valence electron proportion. For most high-temperature alloys, the addition of metal oxide as a refiner into an alloy melt is liable to cause oxygen embrittlement of the product in service, which impairs the mechanical properties of the alloy. And the thermodynamic stability of the existing nitrides and carbides (such as TiC and TiN) is difficult to stably exist in the high-temperature alloy melt. For Nb-based refiners, the common NbC and NbN refiners are difficult to stabilize in high temperature alloy melts due to strong alloying reactions, especially NbN has a melting point of only 2300 ℃. Therefore, improving the stability of NbC and NbN refiners in superalloy melts is one of the concerns in the development of cast superalloy refiners.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-temperature alloy solidification structure refiner and a preparation method and application thereof. According to the invention, the high-temperature alloy solidification structure refiner is designed based on niobium carbide and niobium nitride, and can be used for efficiently refining the solidification structure of a high-temperature alloy casting or ingot and improving the uniformity of the high-temperature alloy solidification structure; c, N element is present in the high-temperature alloy solidification structure refiner, so that the activity of alloying reaction is reduced, and the stability of the refiner in a melt can be improved.
The invention firstly provides a high-temperature alloy solidification structure refiner, which contains three elements of Nb, C and N, and the proportion of each component does not follow the valence measurement; the grain size of the refiner is less than 25 microns.
The invention also provides a preparation method of the high-temperature alloy solidification structure refiner, which comprises the following steps:
(1) ball-milling the mixed powder of the niobium carbide powder and the niobium nitride powder for 0.5-2 h to obtain mixed powder, calcining the mixed powder at 300-450 ℃, cooling to room temperature after calcining, and collecting the powder for later use;
(2) and (2) mechanically alloying the powder obtained in the step (1) in a ball milling tank, and then obtaining the high-temperature alloy solidification structure refiner.
Further, in the step (1), the mass ratio of the niobium carbide powder to the niobium nitride powder is 0.1 to 1.0.
Further, in the step (1), when the powder is ball-milled and mixed, the ball-material ratio range is 15: 1-20: 1, the rotating speed is 100-200 r/min.
Further, in the step (1), the calcining time is 4-8 h.
Further, in the step (2), the ball-to-material ratio in the ball milling tank is 20: 1-30: 1, the rotating speed of the ball milling tank is 200-500 r/min.
Further, the time of mechanical alloying is 18-48 h.
The invention also provides application of the refiner in improving the uniformity of the directional solidification structure of the warm alloy.
Further, the application specifically comprises: and (3) preparing a blank by using a refiner, adding the blank into the high-temperature alloy liquid, electromagnetically stirring, and then pouring into a casting mold to prepare an ingot or a casting.
Furthermore, the amount of the refiner is 0.05-0.5% of the weight of the high-temperature alloy liquid; the temperature of the high-temperature alloy liquid is 80-400 ℃ above the melting point; the electromagnetic stirring time is 1-5 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a novel grain refiner for high-temperature alloy cast ingots or castings, which can improve the uniformity of a high-temperature alloy solidification structure. In the preparation method, the refiner powder can be prepared in large batch by ball milling mechanical alloying, and the production efficiency is higher; in the aspect of the stability of the refiner, the alloying reaction activity of the refiner in the melt is reduced due to the coexistence of C, N elements. Meanwhile, the invention does not relate to the discharge of waste gas, waste water and the like, and does not pollute the environment. In addition, the refiner is added to the superalloy melt without any introduction of harmful elements or impurities.
Drawings
FIG. 1 shows the prepared refiner.
FIG. 2 is a view of a superalloy solidified structure with and without the addition of the refiner (a) at a magnification of 4 times under a body microscope.
FIG. 3 is a view of the superalloy solidified structure obtained in example 3, magnified 4 times under a body microscope.
FIG. 4 is a view of the superalloy solidified structure obtained in example 5 magnified 4 times under a body microscope.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1:
when the mass ratio of niobium carbide/niobium nitride is 0.1, preparing non-stoichiometric niobium carbonitride powder, respectively weighing commercial niobium carbide powder and niobium nitride powder, pouring the commercial niobium carbide powder and niobium nitride powder into a ball milling tank for ball milling and mixing, wherein the ball material ratio is 15: 1, the rotating speed is 100 r/min, the ball milling and powder mixing time is 0.5 hour, then the mixture is poured into a porcelain boat and put into a tube furnace to be calcined for 4 hours at 300 ℃, and the mixture is cooled to the room temperature after the calcination is finished. Pouring the calcined and sintered powder into a ball milling tank for further mechanical alloying, wherein the ball-material ratio is 20: 1, the rotating speed is 200 r/min, and the mechanical alloying time is 18 hours. And finally, sieving the powder subjected to mechanical alloying by a 650-mesh sieve to obtain the high-temperature alloy solidification structure refiner shown in figure 1.
And (4) preparing the prepared high-temperature alloy solidification structure refiner into a blank to obtain a refiner blank. And adding 10g of the refiner blank into 20kg of GH4033 high-temperature alloy with the temperature being higher than the melting point and 80 ℃, electromagnetically stirring for 1 minute, maintaining the temperature, pouring into a casting mold, and preparing an ingot or a casting, namely a high-temperature alloy solidification structure.
FIG. 2 is a view of a superalloy solidified structure with and without the addition of the refiner (a) at a magnification of 4 times under a body microscope. As can be seen from the figure, the grains are significantly refined less adding the refiner.
Example 2:
when the mass ratio of niobium carbide/niobium nitride is 1.0, preparing non-stoichiometric niobium carbonitride powder, respectively weighing commercial niobium carbide powder and niobium nitride powder, pouring the commercial niobium carbide powder and niobium nitride powder into a ball milling tank for ball milling and mixing, wherein the ball material ratio is 20: 1, the rotating speed is 200 r/min, the ball milling and powder mixing time is 2 hours, then the mixture is poured into a porcelain boat and put into a tube furnace to be calcined for 8 hours at the temperature of 450 ℃, and the mixture is cooled to the room temperature after the calcination is finished. Pouring the calcined and sintered powder into a ball milling tank for further mechanical alloying, wherein the ball-material ratio is 30: 1, the rotating speed is 500 r/min, and the mechanical alloying time is 48 hours. And finally, sieving the powder subjected to mechanical alloying by a 3000-mesh sieve to obtain the high-temperature alloy solidification structure refiner.
And (4) preparing the prepared high-temperature alloy solidification structure refiner into a blank to obtain a refiner blank. Adding 100g of the refiner blank into 20kg of GH4043 high-temperature alloy with the temperature of above 400 ℃ of the melting point, electromagnetically stirring for 5 minutes while maintaining the temperature, pouring into a casting mold, and preparing an ingot or a casting, namely a high-temperature alloy solidification structure.
Example 3:
when the mass ratio of niobium carbide/niobium nitride is 0.7, preparing non-stoichiometric niobium carbonitride powder, respectively weighing commercial niobium carbide powder and niobium nitride powder, pouring the commercial niobium carbide powder and niobium nitride powder into a ball milling tank for ball milling and mixing, wherein the ball material ratio is 15: 1, the rotation speed is 200 r/min, the ball milling and powder mixing time is 0.5 hour, then the mixture is poured into a porcelain boat and put into a tube furnace to be calcined for 4 hours at 450 ℃, and the mixture is cooled to room temperature after the calcination is finished. Pouring the calcined and sintered powder into a ball milling tank for further mechanical alloying, wherein the ball-material ratio is 30: 1, the rotating speed is 200 r/min, and the mechanical alloying time is 48 hours. And finally, sieving the powder subjected to mechanical alloying by a 650-mesh sieve to obtain the high-temperature alloy solidification structure refiner.
And (4) preparing the prepared high-temperature alloy solidification structure refiner into a blank to obtain a refiner blank. Adding 100g of the refiner blank into 20kg of GH2036 high-temperature alloy with the temperature being above the melting point and the temperature being 80 ℃, electromagnetically stirring and maintaining the temperature for 5 minutes, pouring into a casting mold, and preparing an ingot or a casting, namely a high-temperature alloy solidification structure.
FIG. 3 is a view of the superalloy solidification structure magnified 4 times under a body microscope. As can be seen from the figure, the grains are significantly refined less adding the refiner.
Example 4:
when the mass ratio of niobium carbide/niobium nitride is 0.2, preparing non-stoichiometric niobium carbonitride powder, respectively weighing commercial niobium carbide powder and commercial niobium nitride powder, pouring the commercial niobium carbide powder and the commercial niobium nitride powder into a ball milling tank for ball milling and powder mixing, wherein the ball material ratio is 20: 1, the rotating speed is 100 r/min, the ball milling and powder mixing time is 2 hours, then the mixture is poured into a porcelain boat and put into a tube furnace to be calcined for 8 hours at 300 ℃, and the mixture is cooled to room temperature after the calcination is finished. Pouring the calcined and sintered powder into a ball milling tank for further mechanical alloying, wherein the ball-material ratio is 20: 1, the rotating speed is 500 r/min, and the mechanical alloying time is 18 hours. And finally, sieving the powder subjected to mechanical alloying by a 3000-mesh sieve to obtain the high-temperature alloy solidification structure refiner.
And (4) preparing the prepared high-temperature alloy solidification structure refiner into a blank to obtain a refiner blank. Adding 10g of the refiner blank into 20kg of GH3039 high-temperature alloy with the temperature of above 400 ℃ of the melting point, electromagnetically stirring and maintaining the temperature for 5 minutes, pouring into a casting mold, and preparing an ingot or a casting, namely a high-temperature alloy solidification structure.
Example 5:
when the mass ratio of niobium carbide/niobium nitride is 0.4, preparing non-stoichiometric niobium carbonitride powder, respectively weighing commercial niobium carbide powder and niobium nitride powder, pouring the commercial niobium carbide powder and niobium nitride powder into a ball milling tank for ball milling and mixing, wherein the ball material ratio is 15: 1, the rotating speed is 200 r/min, the ball milling and powder mixing time is 1.2 hours, then the mixture is poured into a porcelain boat and put into a tube furnace to be calcined for 5 hours at 380 ℃, and the mixture is cooled to the room temperature after the calcination is finished. Pouring the calcined and sintered powder into a ball milling tank for further mechanical alloying, wherein the ball-material ratio is 20: 1, the rotating speed is 280 r/min, and the mechanical alloying time is 28 hours. And finally, sieving the powder subjected to mechanical alloying by a 800-mesh sieve to obtain the high-temperature alloy solidification structure refiner.
And (4) preparing the prepared high-temperature alloy solidification structure refiner into a blank to obtain a refiner blank. Adding 50g of the refiner blank into 20kg of GH1140 high-temperature alloy with the temperature of 120 ℃ above the melting point, electromagnetically stirring for 2 minutes while maintaining the temperature, and pouring into a casting mold to prepare an ingot or a casting, namely a high-temperature alloy solidification structure.
FIG. 4 is a view of a superalloy solidification structure magnified 4 times under a body microscope. As can be seen from the figure, the grains are significantly refined less adding the refiner.
Example 6:
when the mass ratio of niobium carbide/niobium nitride is 0.6, preparing non-stoichiometric niobium carbonitride powder, respectively weighing commercial niobium carbide powder and niobium nitride powder, pouring the commercial niobium carbide powder and niobium nitride powder into a ball milling tank for ball milling and mixing, wherein the ball material ratio is 20: 1, the rotating speed is 180 r/min, the ball milling and powder mixing time is 1.6 hours, then the mixture is poured into a porcelain boat and put into a tube furnace to be calcined for 7 hours at the temperature of 420 ℃, and the mixture is cooled to the room temperature after the calcination is finished. Pouring the calcined and sintered powder into a ball milling tank for further mechanical alloying, wherein the ball-material ratio is 30: 1, the rotating speed is 350 r/min, and the mechanical alloying time is 36 hours. And finally, sieving the powder subjected to mechanical alloying by a 1000-mesh sieve to obtain the high-temperature alloy solidification structure refiner.
And (4) preparing the prepared high-temperature alloy solidification structure refiner into a blank to obtain a refiner blank. Adding 30g of the refiner blank into 20kg of GH1035 high-temperature alloy with the temperature of 1020 ℃ above the melting point, electromagnetically stirring for 1 minute while maintaining the temperature, pouring into a casting mold, and preparing an ingot or a casting, namely a high-temperature alloy solidification structure.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. The preparation method of the high-temperature alloy solidification structure refiner is characterized by comprising the following steps:
(1) ball-milling the mixed powder of the niobium carbide powder and the niobium nitride powder for 0.5-2 h to obtain mixed powder, calcining the mixed powder at 300-450 ℃, cooling to room temperature after calcining, and collecting the powder for later use;
(2) and (2) mechanically alloying the powder obtained in the step (1) in a ball milling tank, and then obtaining the high-temperature alloy solidification structure refiner.
2. The method for producing a superalloy solidification structure refiner as claimed in claim 1, wherein in step (1), the mass ratio of the niobium carbide powder/niobium nitride powder is 0.1 to 1.0.
3. The preparation method of the superalloy solidification structure refiner according to claim 1, wherein in the step (1), when the powder is ball-milled and mixed, the ratio of balls to materials is in a range of 15: 1-20: 1, the rotating speed is 100-200 r/min.
4. The preparation method of the superalloy solidification structure refiner according to claim 1, wherein in the step (1), the calcination time is 4-8 hours.
5. The method for preparing a superalloy solidification structure refiner as claimed in claim 1, wherein in the step (2), the ratio of balls to material in the ball mill pot is 20: 1-30: 1, the rotating speed of the ball milling tank is 200-500 r/min.
6. The method for preparing a refining agent for a solidified structure of a superalloy according to claim 1, wherein the time for mechanical alloying is 18 to 48 hours.
7. The superalloy solidification structure refiner prepared by the preparation method according to any one of claims 1 to 6, wherein the refiner contains three elements of Nb, C and N, and the proportion of each component does not follow the valence measurement; the grain size of the refiner is less than 25 microns.
8. Use of the superalloy solidification structure refiner of claim 7 for improving the homogeneity of the directionally solidified structure of the superalloy.
9. The application according to claim 8, characterized in that it is specifically: adding the refiner into the high-temperature alloy liquid, electromagnetically stirring, and then pouring into a casting mold to prepare an ingot or a casting.
10. The use according to claim 9, wherein the refiner is used in an amount of 0.05-0.5% by weight of the superalloy melt; the temperature of the high-temperature alloy liquid is 80-400 ℃ above the melting point; the electromagnetic stirring time is 1-5 min.
CN202210098759.2A 2022-01-27 2022-01-27 High-temperature alloy solidification structure refiner and preparation method and application thereof Active CN114453567B (en)

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CN101618454A (en) * 2009-07-29 2010-01-06 四川大学 Refining agent containing vanadium for aluminum and aluminum alloy and preparation methods thereof
CN101823141A (en) * 2009-03-04 2010-09-08 沈阳工业大学 Grain-refined high-temperature alloy casting technology
CN102268563A (en) * 2010-06-02 2011-12-07 中国科学院金属研究所 Casting high temperature alloy refiner and high temperature alloy casting method using the same
CN105543524A (en) * 2016-02-01 2016-05-04 华中科技大学 Aluminum alloy grain refiner and preparation method thereof
CN106244838A (en) * 2016-09-21 2016-12-21 燕山大学 Niobium titanium carbon Al-alloy alterant and preparation method thereof
CN111348919A (en) * 2020-03-13 2020-06-30 燕山大学 TiN-NbC composite material and preparation method thereof
CN112143929A (en) * 2020-08-07 2020-12-29 百色学院 Graphene-loaded grain refining material of Al-Mg alloy wire and preparation method thereof
CN113073217A (en) * 2021-03-10 2021-07-06 宁波金田铜业(集团)股份有限公司 Grain refiner and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101417322A (en) * 2007-10-24 2009-04-29 大连核心铸造技术工程研究所 Iron base high-temperature alloy surface refiner
CN101417320A (en) * 2007-10-24 2009-04-29 大连核心铸造技术工程研究所 Cobalt trivalent oxide metal alloy surface refiner
CN101823141A (en) * 2009-03-04 2010-09-08 沈阳工业大学 Grain-refined high-temperature alloy casting technology
CN101618454A (en) * 2009-07-29 2010-01-06 四川大学 Refining agent containing vanadium for aluminum and aluminum alloy and preparation methods thereof
CN102268563A (en) * 2010-06-02 2011-12-07 中国科学院金属研究所 Casting high temperature alloy refiner and high temperature alloy casting method using the same
CN105543524A (en) * 2016-02-01 2016-05-04 华中科技大学 Aluminum alloy grain refiner and preparation method thereof
CN106244838A (en) * 2016-09-21 2016-12-21 燕山大学 Niobium titanium carbon Al-alloy alterant and preparation method thereof
CN111348919A (en) * 2020-03-13 2020-06-30 燕山大学 TiN-NbC composite material and preparation method thereof
CN112143929A (en) * 2020-08-07 2020-12-29 百色学院 Graphene-loaded grain refining material of Al-Mg alloy wire and preparation method thereof
CN113073217A (en) * 2021-03-10 2021-07-06 宁波金田铜业(集团)股份有限公司 Grain refiner and application thereof

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