Rare-earth-doped high-temperature-resistant nickel-based alloy material as well as preparation method and application thereof

Abstract

The invention provides a rare earth doped high-temperature-resistant nickel-based alloy material as well as a preparation method and application thereof. The nickel-based alloy material comprises the following components in percentage by mass: less than or equal to 80wt% of Ni, less than or equal to 25wt% of Cu, less than or equal to 20wt% of Al, less than or equal to 5wt% of Y and inevitable impurities. The Al and Y elements are added into the nickel-based alloy, the content ratio of all the elements is controlled, and all the elements are synergistically compounded, so that the hardness and the surface forming quality of the obtained nickel-based alloy material are obviously improved, the oxidation resistance is high, the internal structure is uniform, development of the field of nickel-based alloy materials is promoted, the preparation process is short, the production cost is low, and the method is suitable for industrial production. The large-scale industrial production can be realized.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high-temperature-resistant seal coating alloy materials, and relates to a nickel-based high-temperature-resistant alloy material, in particular to a rare earth-doped high-temperature-resistant nickel-based alloy material and a preparation method and application thereof. BACKGROUND

[0002] An aero-engine is a highly integrated and precise thermodynamic machine, and is known as the "heart" of an airplane. The manufacturing technology level of the aero-engine is an important symbol for measuring the development strength and comprehensive technology level of an aviation industry of a country. With the rapid development of the aviation industry, higher and higher requirements are put forward for the thrust, efficiency and oil consumption of the aero-engine.

[0003] At present, the seal coating of the seal coating applied to the high-pressure compressor and / or the low-pressure turbine includes a NiCrAl-bentonite seal coating or an AlSi seal coating.

[0004] The oxidation behavior of the NiCrAl-bentonite abradable seal coating at 650°C presents obvious regional difference. On the surface of the coating, the oxidation process follows the evolution sequence of "pointy oxide nucleation→needle-shaped oxide growth→continuous oxide film formation→NiO generation", wherein the pointy and needle-shaped oxides are Al2O3, and the blocky oxide appearing in the later stage is NiO. Inside the coating, oxygen mainly invades along the pores and cracks, and a Cr2O3 layer is preferentially formed, and then a Ni-Cr-Al mixed oxide layer is formed by diffusion of Ni and Al elements. At the interface between the coating and the NiAl bonding layer, the preferential formation of the Cr oxide layer is also observed, and the thickness of the Cr oxide layer continuously increases with the oxidation time, and finally a multilayer structure of the mixed oxide layer is formed. The whole oxidation process is controlled by element diffusion and oxygen partial pressure, wherein the activity order of Al, Cr and Ni is Al>Cr>Ni, and Cr promotes the selective oxidation of Al through the "third element effect". It is worth noting that after 192 hours of oxidation, the hard NiO and α-Al2O3 formed on the surface improve the wear resistance, but significantly aggravate the adhesive wear of the abrasive parts, and weaken the abradability of the coating.

[0005] AlSi sealing coating is mainly used for the abradable sealing coating used in the low-pressure compressor inside. Since the highest working temperature of the inner compressor of the new generation engine can reach 600 DEG C, the existing AlSi coating is prone to falling off, dropping, melting and other problems of insufficient temperature resistance at more than 450 DEG C, and the temperature resistance and corrosion resistance of the AlSi sealing coating need to be improved. By replacing the traditional aluminum (Al) bonding layer with a copper-aluminum (CuAl) alloy, a more stable surface layer rich in copper is formed by using the preferential dissolution characteristics of the CuAl intermediate phase in a specific corrosion environment, thereby effectively inhibiting the further corrosion and oxidation of the coating. With the further increase of temperature, the conventional Cu-Al alloy system is prone to form a loose and porous CuO / Cu2O oxidation layer during high-temperature oxidation, which accelerates the diffusion of oxygen and cannot effectively protect the substrate. At the same time, although the CuAl-Ni / C coating forms an Al2O3 protective layer (such as Al2O3 layer continuous when Al content is greater than or equal to 2%) through the CuAl intermediate phase, the Al2O3 layer may be broken due to grain coarsening or stress concentration when exposed to high temperature for a long time, and the oxidation resistance performance drops sharply.

[0006] In summary, it is necessary to provide a new type of nickel-based alloy material with excellent oxidation resistance and hardness. SUMMARY

[0007] In view of the deficiencies in the prior art, the purpose of the present application is to provide a rare earth doped high-temperature-resistant nickel-based alloy material and its preparation method and application. By adding Al and Y elements to the nickel-based alloy and controlling the content ratio of various elements, the hardness and surface forming quality of the obtained nickel-based alloy material are significantly improved, the oxidation resistance is strong, and the internal organization is uniform, which promotes the development of the field of nickel-based alloy materials, and the preparation process is short, the production cost is low, and large-scale industrial production is possible.

[0008] To achieve the purpose of the present application, the following technical solutions are adopted:

[0009] In a first aspect, the present application provides a rare earth doped high-temperature-resistant nickel-based alloy material, which comprises the following components in mass fraction: Ni≤80wt%, Cu≤25wt%, Al≤20wt%, Y≤5wt% and unavoidable impurities.

[0010] The mass fraction of each metal element in the nickel-based alloy material is not 0.

[0011] For example, the content of Ni in the nickel-based alloy material is ≤80wt%, which can be 80wt%, 70wt%, 60wt%, 50wt% or 40wt%, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0012] The Cu content is less than or equal to 25wt%, for example, can be 25wt%, 20wt%, 15wt%, 10wt% or 5wt%, etc., but not limited to the listed values, other values not listed in the range of values are also applicable;

[0013] The Al content is less than or equal to 20wt%, for example, can be 20wt%, 18wt%, 16wt%, 14wt%, 12wt% or 10wt%, etc., but not limited to the listed values, other values not listed in the range of values are also applicable;

[0014] The Y content is less than or equal to 10wt%, for example, can be 10wt%, 8wt%, 6wt%, 4wt%, 2wt% or 1wt%, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0015] In the present application, by adjusting the content ratio between Al and Y elements, Y elements play a role in grain boundary purification and grain refinement, and Al elements are activated to promote the formation of a protective oxide film, thereby improving the hardness and oxidation resistance of the nickel-based alloy material, solving the problems of low hardness and poor oxidation resistance of the nickel-based alloy material.

[0016] As a preferred technical solution of the present application, the nickel-based alloy material includes the following components in mass fraction: Ni 60-80wt%, Cu≤15wt%, Al≤10wt% and Y≤5wt%.

[0017] Preferably, the Y content in the nickel-based alloy material is 0.1-3wt%, for example, can be 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0018] In the present application, by optimizing the content of Y element to ensure the oxidation resistance of the nickel-based alloy material, while having higher hardness, if the content of Y element is too low, the oxidation resistance of the obtained nickel-based alloy material will be poor, and if the content is too high, the oxidation resistance and hardness of the obtained nickel-based alloy material will be poor.

[0019] In a second aspect, the present application provides a preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material as described in the first aspect, the preparation method comprising the following steps:

[0020] (1) Mix Ni powder, Cu powder, Al powder and Y powder according to the formula amount to obtain mixed raw materials;

[0021] (2) Hot-press sintering the mixed raw materials obtained in step (1) to obtain a sintered matrix;

[0022] (3) annealing the sintered substrate obtained in step (2) to obtain the rare earth doped high-temperature-resistant nickel-based alloy material.

[0023] The preparation method provided by the application first uniformly mixes the single-element powders of the components, then realizes the alloying of the metal powders through hot-pressing sintering, and finally improves the alloy performance through annealing treatment.

[0024] As a preferred technical solution of the application, the purity of the Ni powder, the Cu powder, the Al powder and the Y powder in step (1) is all greater than or equal to 99.95%, for example, can be 99.95%, 99.96%, 99.97%, 99.98% or 99.99%, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0025] Preferably, the average particle size of the mixed raw materials in step (1) is 20-100 μm, for example, can be 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 80 μm or 100 μm, but is not limited to the listed values, and other values not listed in the value range are also applicable; preferably, 20-50 μm.

[0026] The application is beneficial to the densification of hot-pressing sintering by optimizing the average particle size of the mixed raw materials, can improve the comprehensive performance of the multi-main-element alloy, and reduce the introduction of oxygen and impurities in the forming process; when the average particle size of the mixed raw materials is too small, the specific surface area increases significantly, resulting in a substantial increase in the oxygen content and impurity content in the initial mixed raw materials; and when the average particle size is too large, it will hinder the densification sintering process of the alloy and affect the final density.

[0027] Preferably, the mixing in step (1) includes: performing acoustic resonance mixing under a protective atmosphere.

[0028] Preferably, the protective atmosphere includes argon and / or nitrogen.

[0029] Preferably, the filling ratio of the acoustic resonance mixing is 60-100%, for example, can be 60%, 70%, 80%, 90% or 100%, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0030] Preferably, the frequency of the acoustic resonance mixing is 50-80 Hz, for example, can be 50 Hz, 55 Hz, 60 Hz, 65 Hz, 70 Hz, 75 Hz or 80 Hz, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0031] Preferably, the acceleration of the acoustic resonance mixing is 40-80g, for example, it can be 40g, 50g, 60g, 70g or 80g, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0032] Preferably, the time of the acoustic resonance mixing is 10-90min, for example, it can be 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min or 90min, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0033] The present application can improve the powder mixing rate by the acoustic resonance mixing, control the powder mixing humidity, avoid the influence of the powder mixing temperature rise on the purity of the mixed raw materials, and thus affect the product purity.

[0034] Preferably, the step (2) further comprises a compaction treatment on the mixed raw materials before the hot-pressing sintering to obtain a pre-pressed blank.

[0035] As a preferred technical solution of the present application, the hot-pressing sintering in step (2) is performed in a vacuum environment.

[0036] Preferably, the vacuum degree of the vacuum environment is 1.0x10 -4 ~1.0x10 -3 Pa, for example, it can be 1.0x10 -4 Pa, 3.0x10 -4 Pa, 5.0x10 -4 Pa, 7.0x10 -4 Pa or 1.0x10 -3 Pa, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0037] As a preferred technical solution of the present application, the hot-pressing sintering in step (2) comprises a first temperature rising treatment, a second temperature rising treatment, a pressurizing treatment, a temperature and pressure maintaining treatment and a temperature lowering treatment performed in sequence.

[0038] Preferably, the first temperature rising treatment comprises: rising the temperature to 600-800℃ at a temperature rising rate of 5-15℃ / min, wherein the temperature rising rate is 5-15℃ / min, for example, it can be 5℃ / min, 7℃ / min, 9℃ / min, 11℃ / min, 13℃ / min or 15℃ / min, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable; and the terminal temperature of the temperature rising is 600-800℃, for example, it can be 600℃, 650℃, 700℃, 750℃ or 800℃, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0039] In the present application, the appropriate heating rate in the first heating treatment process helps the ordered growth of the crystal grains and the discharge of pores, thereby improving the density and surface quality of the nickel-based alloy; further, too fast a heating rate will lead to an increase in internal pores, affecting the density; too slow a heating rate will reduce the effect of hot-pressing sintering and damage the quality of the final alloy. In addition, too low a terminal temperature of the first heating treatment will not trigger the sintering reaction; too high a terminal temperature will reduce the density of the obtained alloy material.

[0040] Preferably, the second heating treatment comprises: heating to 800-1500℃ at a heating rate of 3-7℃ / min; wherein the heating rate is 3-7℃ / min, for example, it can be 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min or 7℃ / min, etc., but not limited to the listed values, other values not listed in the value range are also applicable; the terminal temperature of heating is 800-1500℃, for example, it can be 800℃, 1000℃, 1200℃, 1400℃ or 1500℃, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0041] In the present application, the appropriate heating rate and terminal temperature in the second heating treatment process can further improve the density, hardness and surface quality of the obtained alloy material; further, if the heating rate or the terminal temperature in the second heating treatment is too low, it will lead to insufficient hot-pressing sintering, thereby affecting the product quality; if the heating rate or the terminal temperature in the second heating is too high, it will lead to an increase in the pores of the obtained alloy and a decrease in hardness.

[0042] Preferably, the pressurizing process comprises a first pressurizing and a second pressurizing performed in sequence.

[0043] Preferably, the first pressurizing is: pressurized to 25-30MPa within 1h, for example, it can be 25MPa, 26MPa, 27MPa, 28MPa, 29MPa or 30MPa, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0044] Preferably, the second pressurizing is: pressurized to 50-55MPa within 1h, for example, it can be 50MPa, 51MPa, 52MPa, 53MPa, 54MPa or 55MPa, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0045] In the present application, the appropriate end pressure in the pressurization process can effectively increase the contact area between particles, promote the densification sintering of the raw material, reduce pores, voids, and eliminate holes, while enhancing the bonding strength between grains, so that the density, hardness, bending strength, and fracture toughness of the obtained nickel-based alloy material are improved. Further, if the end pressure is too low, the number of holes in the nickel-based alloy material will increase, which will lead to a decrease in hardness and surface quality. If the end pressure is too high, the grain size will increase, which is not conducive to the improvement of the comprehensive performance of the alloy.

[0046] Preferably, the holding and pressure maintaining process lasts for 0.5-2h, for example, it can be 0.5h, 0.8h, 1.1h, 1.4h, 1.7h, or 2h, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable.

[0047] Preferably, the cooling process includes cooling to 600-800℃ at a cooling rate of 10-20℃ / min, wherein the cooling rate is 10-20℃ / min, for example, it can be 10℃ / min, 12℃ / min, 14℃ / min, 16℃ / min, 18℃ / min, or 20℃ / min, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable; the final temperature of cooling is 600-800℃, for example, it can be 600℃, 650℃, 700℃, 750℃, or 800℃, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable.

[0048] Preferably, the cooling process is accompanied by a pressure relief process.

[0049] Preferably, the pressure relief process is performed 10-30min after the start of the cooling process, for example, it can be 10min, 15min, 20min, 25min, or 30min, etc., but is not limited to the listed values, and other values not listed within the value range are also applicable.

[0050] Preferably, the cooling process is accompanied by a pressure relief process.

[0051] Preferably, the cooling process is accompanied by a pressure relief process.

[0052] The present application helps to release part of thermal stress inside the material and promote the migration and discharge of pores inside the material by optimizing the cooling rate and end cooling temperature of the cooling treatment and combining with subsequent furnace cooling, thereby effectively reducing the pores in the obtained multi-principal element alloy and improving the density thereof; if the cooling rate is too fast, larger thermal stress will be induced, thereby causing the generation of participating stress or micro cracks inside the material.

[0053] As a preferred technical solution of the present application, the annealing temperature of the annealing treatment in step (3) is 500-950℃, for example, it can be 500℃, 600℃, 700℃, 800℃, 900℃ or 950℃, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0054] Preferably, the holding time of the annealing treatment in step (3) is 0.5-3h, for example, it can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h, etc., but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0055] As a preferred technical solution of the present application, the preparation method of the rare earth doped high-temperature resistant nickel-based alloy material provided in the second aspect of the present application comprises the following steps:

[0056] (1) Under a protective atmosphere, the Ni powder, Cu powder, Al powder and Y powder are mixed by sound resonance according to the formula amount to obtain mixed raw materials with an average particle size of 20-100μm;

[0057] The purity of the Ni powder, Cu powder, Al powder and Y powder is all ≥99.95%;

[0058] The filling ratio of the sound resonance mixing is 60-100%, the frequency is 50-80Hz, the acceleration is 40-80g, and the time is 10-90min;

[0059] (2) The mixed raw materials obtained in step (1) are subjected to hot-pressing sintering under a vacuum environment of 1.0×1.0 -4 ~1.0×1.0 -3 Pa to obtain a sintered matrix;

[0060] The hot-pressing sintering comprises first heating treatment, second heating treatment, pressurizing treatment, holding and pressure maintaining treatment, cooling treatment and furnace cooling in sequence;

[0061] The first temperature rising treatment comprises: rising the temperature to 600-800 DEG C at a temperature rising rate of 5-15 DEG C / min; the second temperature rising treatment comprises: rising the temperature to 800-1500 DEG C at a temperature rising rate of 3-7 DEG C / min; the pressure treatment comprises: pressurizing to 25-50 MPa within 1-2 h; the time of the temperature and pressure maintaining treatment is 0.5-2 h; the temperature dropping treatment comprises: dropping the temperature to 600-800 DEG C at a temperature dropping rate of 10-20 DEG C / min; the temperature dropping treatment is accompanied by a pressure releasing treatment, and the pressure releasing treatment is performed after 10-30 min of the temperature dropping treatment; the end temperature of the furnace cooling is 20-25 DEG C.

[0062] (3) annealing the sintered substrate obtained in step (2) to obtain the rare earth doped high-temperature-resistant nickel-based alloy material;

[0063] The annealing temperature of the annealing treatment is 500-950 DEG C, and the holding time is 0.5-3 h.

[0064] In the second aspect, the application provides an application of the rare earth doped high-temperature-resistant nickel-based alloy material as described in the first aspect, and the rare earth doped high-temperature-resistant nickel-based alloy material is used as a sealing coating metal phase.

[0065] The nickel-based alloy material has wide application, and is mainly used in the fields of aerospace or automobile manufacturing, such as aero-engine compressor, turbine blade and rotor-shell matching parts, and has great significance for the development of the sealing coating field.

[0066] The numerical range of the application includes not only the point values exemplified above, but also any point values between the above numerical ranges which are not exemplified, and the specific point values included in the range are not listed again in the application for the sake of brevity and simplicity.

[0067] Compared with the prior art, the application has the following beneficial effects:

[0068] (1) The application adjusts and controls the content ratio between Al element and Y element, so that the Y element plays a role of grain boundary purification and grain refinement, and the Al element is activated to promote the formation of a protective oxidation film, the hardness and the oxidation resistance of the nickel-based alloy material are improved, the problems of low hardness and poor oxidation resistance of the nickel-based alloy material are solved, and the nickel-based alloy material has application potential in the sealing coating field;

[0069] (2) The nickel-based alloy material provided by the application can be widely applied in the fields of aerospace or automobile manufacturing, BRIEF DESCRIPTION OF DRAWINGS

[0070] Figure 1 The XRD graph of the nickel-based alloy material provided for the example 1, 4-7 and the comparative example 1 of the application

[0071] Figure 2 Hardness comparison chart of nickel-based alloy materials provided for the present embodiment 1, 4-7 and comparative example 1;

[0072] Figure 3 Oxidation weight gain comparison chart of nickel-based alloy materials provided for the present embodiment 1, 4-7 and comparative example 1 under 500℃ cyclic oxidation for 100h;

[0073] Figure 4 XRD chart of nickel-based alloy materials provided for the present embodiment 1, 4-7 and comparative example 1 under 500℃ cyclic oxidation for 100h. DETAILED DESCRIPTION

[0074] The technical solutions of the present application will be further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0075] The content of each element in the rare earth doped high temperature resistant nickel-based alloy material described in the following examples and comparative examples is accurate to 0.1 according to the rounding principle, and the unavoidable impurity content is ≤0.05wt%.

[0076] Embodiment 1

[0077] The present embodiment provides a rare earth doped high temperature resistant nickel-based alloy material, which comprises the following components in mass fraction: Ni 79.5wt%, Cu 12wt%, Al 8wt%, Y 0.5wt% and unavoidable impurities.

[0078] The preparation method of the rare earth doped high temperature resistant nickel-based alloy material (denoted as 0.5Y) comprises the following steps:

[0079] (1) Under argon protective atmosphere, mix Ni powder, Cu powder, Al powder with purity of 99.99% and YH 2-3 powder with purity of 99.97% according to the formula amount by acoustic resonance to obtain mixed raw materials with an average particle size of 20-50μm;

[0080] Among them, the filling ratio of acoustic resonance mixing is 80%, the frequency is 55Hz, the acceleration is 60g, and the time is 30min;

[0081] (2) Under a vacuum environment of 8.0×1.0 -4 Pa, the mixed raw materials obtained in step (1) are subjected to hot-pressing sintering to obtain a sintered matrix;

[0082] Among them, the hot-pressing sintering comprises first heating treatment, second heating treatment, pressure treatment, holding treatment, cooling treatment and furnace cooling in sequence;

[0083] the first temperature rising process comprises rising to 800℃ at a temperature rising rate of 9℃ / min; the second temperature rising process comprises rising to 1100℃ at a temperature rising rate of 5℃ / min; the pressurizing process comprises pressurizing to 25MPa once within 1h and then pressurizing to 50MPa again within 60min; the time of the temperature and pressure maintaining process is 1h; the temperature falling process comprises falling to 800℃ at a temperature falling rate of 15℃ / min; the temperature falling process is accompanied by a depressurizing process, and the depressurizing process is performed 10min after the temperature falling process starts; the endpoint temperature of the furnace cooling is 25℃;

[0084] (3) annealing the sintered substrate obtained in step (2) to obtain the rare earth doped high-temperature-resistant nickel-based alloy material;

[0085] The annealing temperature of the annealing process is 800℃, and the holding time is 1h.

[0086] Example 2

[0087] The rare earth doped high-temperature-resistant nickel-based alloy material comprises the following components in mass fraction: Ni 72wt%, Cu 20.8wt%, Al 6wt%, Y 1.2wt% and inevitable impurities.

[0088] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material comprises the following steps:

[0089] (1) under an argon protective atmosphere, mixing Ni powder, Cu powder, Al powder and Y powder according to the formula amount by acoustic resonance to obtain mixed raw materials with an average particle size of 50-100μm;

[0090] The purity of the Ni powder, the Cu powder and the Al powder is 99.99%, and the purity of the Y powder is 99.97%;

[0091] The filling ratio of the acoustic resonance mixing is 60%, the frequency is 50Hz, the acceleration is 40g, and the time is 90min;

[0092] (2) under a vacuum environment of 1.0×1.0 -4 Pa, hot-press sintering the mixed raw materials obtained in step (1) to obtain a sintered substrate;

[0093] The hot-press sintering comprises a first temperature rising process, a second temperature rising process, a pressurizing process, a temperature and pressure maintaining process, a temperature falling process and furnace cooling in sequence;

[0094] The first temperature rising process comprises rising to 600℃ at a temperature rising rate of 5℃ / min; the second temperature rising process comprises rising to 800℃ at a temperature rising rate of 3℃ / min; the pressurizing process comprises pressurizing to 30MPa once within 1h and then pressurizing to 55MPa twice within 1h; the time of the temperature and pressure maintaining process is 2h; the temperature dropping process comprises dropping to 600℃ at a temperature dropping rate of 10℃ / min; the temperature dropping process is accompanied by a pressure releasing process, and the pressure releasing process is performed 30min after the temperature dropping process starts; the end temperature of the furnace cooling is 20℃;

[0095] (3) annealing the sintered substrate obtained in step (2) to obtain the rare earth doped high-temperature-resistant nickel-based alloy material;

[0096] The annealing temperature of the annealing process is 500℃, and the holding time is 3h.

[0097] Example 3

[0098] The rare earth doped high-temperature-resistant nickel-based alloy material comprises the following components in mass fraction: Ni 80wt%, Cu 10wt%, Al 7.5wt% and Y 2.5wt%.

[0099] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material comprises the following steps:

[0100] (1) under a nitrogen protective atmosphere, mixing Ni powder, Cu powder, Al powder and Y powder according to the formula amount by acoustic resonance to obtain mixed raw materials with an average particle size of 20-40μm;

[0101] The purity of the Ni powder, the Cu powder and the Al powder is 99.99%, and the purity of the Y powder is 99.96%;

[0102] The filling ratio of the acoustic resonance mixing is 95%, the frequency is 80Hz, the acceleration is 80g, and the time is 10min;

[0103] (2) under a vacuum environment of 1.0×1.0 -3 Pa, hot-press sintering the mixed raw materials obtained in step (1) to obtain a sintered substrate;

[0104] The hot-press sintering comprises a first temperature rising process, a second temperature rising process, a pressurizing process, a temperature and pressure maintaining process, a temperature dropping process and furnace cooling in sequence;

[0105] The first temperature increasing process comprises increasing the temperature to 800℃ at a temperature increasing rate of 15℃ / min; the second temperature increasing process comprises increasing the temperature to 1500℃ at a temperature increasing rate of 7℃ / min; the pressurizing process comprises pressurizing to 28MPa once within 1h and pressurizing to 53MPa twice within 1h; the time of the temperature and pressure maintaining process is 0.5h; the temperature decreasing process comprises decreasing the temperature to 800℃ at a temperature decreasing rate of 20℃ / min; the temperature decreasing process is accompanied by a pressure releasing process, and the pressure releasing process is performed 20min after the temperature decreasing process is started; the end temperature of the furnace cooling is 22℃;

[0106] (3) annealing the sintered substrate obtained in step (2) to obtain the rare earth doped high-temperature-resistant nickel-based alloy material;

[0107] The annealing temperature of the annealing process is 950℃, and the holding time is 0.5h.

[0108] Example 4

[0109] The rare earth doped high-temperature-resistant nickel-based alloy material provided in the example comprises the following components in mass fraction: Ni 79wt%, Cu 12wt%, Al 8wt%, Y 1wt% and inevitable impurities.

[0110] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material is the same as that in Example 1, and the rare earth doped high-temperature-resistant nickel-based alloy material is recorded as 1Y.

[0111] Example 5

[0112] The rare earth doped high-temperature-resistant nickel-based alloy material provided in the example comprises the following components in mass fraction: Ni 77wt%, Cu 12wt%, Al 8wt%, Y 3wt% and inevitable impurities.

[0113] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material is the same as that in Example 1, and the rare earth doped high-temperature-resistant nickel-based alloy material is recorded as 3Y.

[0114] Example 6

[0115] The rare earth doped high-temperature-resistant nickel-based alloy material provided in the example comprises the following components in mass fraction: Ni 75wt%, Cu 12wt%, Al 8wt%, Y 5wt% and inevitable impurities.

[0116] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material is the same as that in Example 1, and the rare earth doped high-temperature-resistant nickel-based alloy material is recorded as 5Y.

[0117] Example 7

[0118] The embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, which comprises the following components in mass fraction: 70wt% of Ni, 12wt% of Cu, 8wt% of Al, 10wt% of Y and inevitable impurities.

[0119] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material is the same as that in the embodiment 1, and the rare earth doped high-temperature-resistant nickel-based alloy material is recorded as 10Y.

[0120] Embodiment 8

[0121] The embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, and the preparation method of the nickel-based alloy material is only different from that in the embodiment 1 in that:

[0122] The ball milling mixing is adopted in the step (1) in the embodiment; and the ball-to-material ratio of the ball milling mixing is 3:1.

[0123] Embodiment 9

[0124] The embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, and the preparation method of the nickel-based alloy material is only different from that in the embodiment 1 in that:

[0125] The heat pressure sintering in the step (2) is adjusted to be sequentially performed in the following steps: temperature increasing treatment, pressure increasing treatment, temperature and pressure maintaining treatment, temperature decreasing treatment and furnace cooling; and the temperature increasing treatment is performed at a temperature increasing rate of 5 ℃ / min to 1100 ℃.

[0126] Embodiment 10

[0127] The embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, and the preparation method of the nickel-based alloy material is only different from that in the embodiment 1 in that:

[0128] The temperature increasing rate of the first temperature increasing treatment is adjusted to be 3 ℃ / min, and the temperature increasing rate of the second temperature increasing treatment is adjusted to be 2 ℃ / min.

[0129] Embodiment 11

[0130] The embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, and the preparation method of the nickel-based alloy material is only different from that in the embodiment 1 in that:

[0131] The temperature increasing rate of the first temperature increasing treatment is adjusted to be 18 ℃ / min, and the temperature increasing rate of the second temperature increasing treatment is adjusted to be 10 ℃ / min.

[0132] Embodiment 12

[0133] The present embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, and a preparation method of the nickel-based alloy material is different from that of embodiment 1 only in that:

[0134] In the present embodiment, the end pressure of the pressurization treatment is adjusted to 20 MPa.

[0135] Example 13

[0136] The present embodiment provides a rare earth doped high-temperature-resistant nickel-based alloy material, and a preparation method of the nickel-based alloy material is different from that of embodiment 1 only in that:

[0137] In the present embodiment, the end pressure of the pressurization treatment is adjusted to 60 MPa.

[0138] Comparative Example 1

[0139] The present comparative example provides a rare earth doped high-temperature-resistant nickel-based alloy material, and the nickel-based alloy material comprises the following components in mass fraction: Ni 80wt%, Cu 12wt%, Al 8wt% and inevitable impurities.

[0140] The preparation method of the rare earth doped high-temperature-resistant nickel-based alloy material is the same as that of embodiment 1, and the rare earth doped high-temperature-resistant nickel-based alloy material is recorded as 0Y.

[0141] Performance detection:

[0142] The high-temperature-resistant nickel-based alloy materials provided by the above embodiments and comparative examples are subjected to hardness test and 100h cyclic oxidation resistance test, and the results are shown in Table 1;

[0143] Among them, the XRD patterns of the nickel-based alloy materials provided by embodiments 1, 4-7 and comparative example 1 are shown in Figure 1 , the hardness comparison chart is shown in Figure 2 , the oxidation weight gain comparison chart of 100h cyclic oxidation at 500℃ is shown in Figure 3 , and the XRD pattern of 100h cyclic oxidation at 500℃ is shown in Figure 4 .

[0144] Table 1

[0145]

[0146] According to Table 1 and Figures 1-4 , the following points can be known:

[0147] (1) According to the comprehensive analysis of embodiments 1-3, the nickel-based alloy material obtained by using the preparation method provided by the present application has excellent hardness and oxidation resistance, and has application potential in the field of severe coating;

[0148] (2) Comprehensive analysis of examples 1, 4-7 and comparative example 1 shows that when the content of Y is higher than 3wt%, the hardness and oxidation resistance of the nickel-based alloy material gradually decrease with the increase of the content of Y element, further proving the necessity of optimizing the content of Y element;

[0149] When the addition of Y element is omitted, non-dense copper oxide and nickel oxide are generated during the oxidation process, and the Al element cannot form a continuous and dense oxide film to protect the alloy from oxidation;

[0150] (3) Comprehensive analysis of examples 1 and examples 8-13 shows that the selection of process parameters in the preparation method of the application will also affect the performance of the nickel-based alloy material;

[0151] If the acoustic resonance mixing is adjusted to ball milling mixing, the mixing uniformity will decrease, and there will still be a large amount of binder or active component agglomerates in the powder, resulting in holes, composition segregation in the subsequent sintered body, and large performance fluctuations;

[0152] If the segmented temperature rising treatment is adjusted to one-time temperature rising treatment (such as example 9), the densification degree of the alloy will decrease, the porosity will increase, and the grain will be uneven;

[0153] If the temperature rising rate of the first and second temperature rising treatments is too low, the densification efficiency will decrease, and the grain will abnormally grow, resulting in a decrease in hardness, and if it is too high, the alloy surface will be densified in advance, closed pores will be formed inside, and the relative density will decrease;

[0154] If the end pressure of the pressure treatment is too low, the density will be low, the porosity will be high, the strength will be poor, and the size will be unstable, and if it is too high, the grain will be coarse, the hardness will decrease, the composition will segregate, the graphite mold will be easy to crack, and the cost will increase;

[0155] In summary, by adding Al and Y elements to the nickel-based alloy and controlling the content ratio of various elements, the hardness and surface forming quality of the obtained nickel-based alloy material are significantly improved, the oxidation resistance is strong, and the internal organization is uniform, which promotes the development of the field of nickel-based alloy materials, and the preparation process is short, the production cost is low, and large-scale industrial production is possible.

[0156] The applicant declares that the above is only a specific embodiment of the application, but the protection scope of the application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the application can be easily thought of by those skilled in the art, and all fall within the protection scope and disclosure scope of the application.

Claims

1. A rare earth doped high temperature nickel-base alloy material, characterized in that, The nickel-based alloy material comprises the following components in mass fraction: Ni≤80wt%, Cu≤25wt%, Al≤20wt%, Y≤5wt%, and inevitable impurities.

2. The rare earth doped refractory nickel-base alloy material of claim 1, wherein, The nickel-based alloy material comprises the following components in mass fraction: Ni 60-80wt%, Cu≤15wt%, Al≤10wt%, and Y≤5wt%. Preferably, the Y content in the nickel-based alloy material is 0.1-3wt%.

3. A method of producing a rare earth doped high temperature nickel-based alloy material as claimed in claim 1 or 2, characterized in that, The preparation method comprises the following steps: (1) mixing Ni powder, Cu powder, Al powder, and Y powder according to the formula amount to obtain mixed raw materials; (2) performing hot-pressing sintering on the mixed raw materials obtained in step (1) to obtain a sintered substrate; (3) performing annealing treatment on the sintered substrate obtained in step (2) to obtain the rare earth doped high-temperature-resistant nickel-based alloy material.

4. The production method according to claim 3, characterized by, The purity of the Ni powder, Cu powder, Al powder, and Y powder in step (1) is all ≥99.95%. Preferably, the average particle size of the mixed raw materials in step (1) is 20-100μm, preferably 20-50μm. Preferably, the mixing in step (1) comprises: performing acoustic resonance mixing under a protective atmosphere. Preferably, the protective atmosphere comprises argon and / or nitrogen. Preferably, the filling ratio of the acoustic resonance mixing is 60-100%. Preferably, the frequency of the acoustic resonance mixing is 50-80Hz. Preferably, the acceleration of the acoustic resonance mixing is 40-80g. Preferably, the time of the acoustic resonance mixing is 10-90min.

5. The production method according to claim 3 or 4, characterized by, The hot-pressing sintering in step (2) is performed in a vacuum environment. Preferably, the vacuum degree of the vacuum environment is 1.0 x 1.0 -4 Pa. Preferably, the vacuum degree of the vacuum environment is 1.0 x 1.0 -3 Pa.

6. The method of any one of claims 3-5, wherein, The hot-pressing sintering in step (2) comprises sequentially performed first temperature rising treatment, second temperature rising treatment, pressure increasing treatment, temperature and pressure maintaining treatment, and temperature decreasing treatment.

7. The production method according to claim 6, wherein The first temperature rising treatment comprises: rising the temperature to 600-800℃ at a temperature rising rate of 5-15℃ / min. Preferably, the second temperature rising treatment comprises: rising the temperature to 800-1500℃ at a temperature rising rate of 3-7℃ / min. Preferably, the pressure increasing process comprises sequentially performed first pressure increasing and second pressure increasing. Preferably, the first pressure increasing is: increasing the pressure to 25-30MPa within 1h. Preferably, the second pressure increasing is: increasing the pressure to 50-55MPa within 1h. Preferably, the temperature and pressure maintaining treatment is performed for 0.5-2h. Preferably, the temperature decreasing treatment comprises: decreasing the temperature to 600-800℃ at a temperature decreasing rate of 10-20℃ / min.

8. The preparation method according to claim 7, characterized in that, The temperature decreasing treatment is also accompanied by pressure decreasing treatment. Preferably, the pressure decreasing treatment is performed 10-30min after the temperature decreasing treatment starts. Preferably, the temperature decreasing treatment is also followed by furnace cooling. Preferably, the end point temperature of the furnace cooling is 20-25℃.

9. The method of any one of claims 3-8, wherein, The annealing temperature of the annealing treatment in step (3) is 500-950℃. Preferably, the temperature maintaining time of the annealing treatment in step (3) is 0.5-3h.

10. Use of a rare earth doped high temperature nickel base alloy material as claimed in claim 1 or 2, characterized in that, The rare earth doped high-temperature-resistant nickel-based alloy material is used as a sealing coating metal phase.

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