阅读说明：本技术 一种航空航天用耐高温抗氧化镍基合金材料及其制备方法和应用 (High-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace and preparation method and application thereof ) 是由 鲁永林 巨佳 唐家浩 胡行超 强新发 高俊 吴炎东 殷想 杨陆滋柏 于 2021-09-24 设计创作，主要内容包括：本发明公开了一种航空航天用耐高温抗氧化镍基合金材料,包括以下质量百分含量的元素组分：Si：13.5～15.4%；Fe：1.5～3.9%；Ti：10.3～16.7%；C：0.1～0.4%；Al：2.2～5.8%；Ni：余量。本发明还公开了一种航空航天用耐高温抗氧化镍基合金材料的制备方法及其在航空航天用镍基合金中的应用。本发明的镍基合金材料具有特殊的微观结构,即晶粒外层由超细三维网状中间相层包裹。Ti-(4)Ni-(4)Si-(7)相属于高致密度组织,一方面能够有效防止氧向材料内部扩散发生氧化。另一方面,相中活性元素Ti和Si能够夺取少量扩散进去的氧,形成稳定结合的氧化物,让该材料具有非常优异的抗氧化性能。(The invention discloses a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace, which comprises the following element components in percentage by mass: si: 13.5 to 15.4 percent; fe: 1.5-3.9%; ti: 10.3 to 16.7 percent; c: 0.1-0.4%; al: 2.2-5.8%; ni: and (4) the balance. The invention also discloses a preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace and application of the high-temperature-resistant and oxidation-resistant nickel-based alloy material in the nickel-based alloy for aerospace. The nickel-based alloy material has a special microstructure, namely the outer layer of crystal grains is wrapped by a superfine three-dimensional reticular mesophase layer. Ti 4 Ni 4 Si 7 Belongs to a high-density tissue, and on one hand, can effectively prevent oxygen from diffusing into the material to generate oxidation. On the other hand, active elements Ti and Si in the phase can take a small amount of diffused oxygen to form stably combined oxide, so that the material has very excellent oxidation resistance.)

1. The high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace is characterized by comprising the following components in parts by weight: comprises the following element components in percentage by mass:

。

2. the high-temperature-resistant oxidation-resistant nickel for aerospace use according to claim 1The base alloy material is characterized in that: the microstructure of the material consists of ultrafine net Ti₄Ni₄Si₇And (4) wrapping the intermediate phase.

3. The high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace according to claim 2, wherein: the crystal grains contain Ti oxide and Si oxide.

4. The preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace according to any one of claims 1 to 3, wherein the preparation method comprises the following steps: the method comprises the following steps:

s1, proportioning and weighing the components according to the proportion, and then cleaning and drying the components;

s2, placing the dried Ni, Ti, Fe and C in a crucible for vacuum induction smelting, starting magnetic stirring after complete cleaning, and continuing smelting until elements are uniformly distributed to obtain a solution;

s3, adding Si and Al into the uniformly smelted melt, continuing smelting and heating until the melt is completely cleared for the second time, and then stopping heating to obtain an alloy melt;

s4, pouring the smelted alloy melt into a nitrogen-filled air pressure casting heat preservation furnace for heat preservation;

s5, casting the molten steel in the heat preservation furnace into a liquid die forging machine die for liquid die forging, and demolding the alloy material after forging;

s6, placing the demolded alloy material in a vacuum heat treatment furnace for performance heat treatment, and then obtaining the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace.

5. The preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace according to claim 4, wherein the preparation method comprises the following steps: in S2, the smelting temperature is 1950-2000 ℃, the smelting time is 35-55 min, and the stirring time is 15-30 min.

6. The preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace according to claim 4, wherein the preparation method comprises the following steps: in S3, the smelting temperature is 1950-2000 ℃, and the smelting time is 25-40 min.

7. The preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace according to claim 4, wherein the preparation method comprises the following steps: and in S4, the heat preservation temperature is 1750-1800 ℃, and the heat preservation time is 15-35 min.

8. The preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace according to claim 4, wherein the preparation method comprises the following steps: s5, preheating the die to 400-450 ℃ before casting, wherein the die forging temperature is 1650-1680 ℃, the pressurizing speed is 70-140 mm/S, the mold filling time is 6-9S, the specific pressure is 210-280 Mpa, the pressure maintaining time is 100-180S, and the demolding temperature is 1200-1250 ℃.

9. The preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace according to claim 4, wherein the preparation method comprises the following steps: in S6, the performance heat treatment is divided into three steps of solid solution, high temperature aging and low temperature aging:

s01: solid solution: preserving the temperature for 5-8 h at 1420-1480 ℃, and then air-cooling to room temperature;

s02: high-temperature aging: preserving heat for 15-19 h at 1200-1250 ℃, and then cooling to room temperature at a cooling rate of 15-23 ℃/s;

s03: low-temperature aging: keeping the temperature of 630-680 ℃ for 20-24 h, and then cooling to room temperature at a cooling rate of 6-9 ℃/s.

10. The application of the high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace according to any one of claims 1-3 in the nickel-based alloy for aerospace.

Technical Field

The invention relates to a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace and a preparation method and application thereof, belonging to the technical field of aerospace.

Background

Along with the development of the related industries of aerospace and aviation in China, the demand of nickel-based alloy steel products with high strength and oxidation resistance and corrosion resistance at high temperature is increasing in matched engineering projects. However, the nickel-based alloy steel and products thereof in China have a great gap with American ASME technical specifications, most of the nickel-based alloys on domestic important equipment depend on import, and occupy a great amount of foreign exchanges in China. In the past, because the domestic manufacturing standard of the matched products of the nickel-based alloy is absent, the products mainly take nickel element as a basic material, and are different from stainless steel matched products taking iron element as a basic material, the mechanical property, the high temperature resistance and the corrosion resistance of the products are far higher than those of the stainless steel matched products, the manufacturing difficulty of the products is far higher than that of the stainless steel matched products, and the products are basically in a blank state in China. Along with the wide application of the nickel-based alloy matching products in China, the localization of the products is also great tendency, the high-temperature-resistant, oxidation-resistant and corrosion-resistant nickel-based alloy part products which can be applied to aerospace and matching engineering thereof are researched and developed, the localization is realized, and the technology and the economic significance are great.

Currently, nickel-based alloys have been widely used in aerospace and its complement because of their excellent high temperature mechanical properties. However, the working conditions of the application places are complex, and the nickel-based alloy often faces the actual working conditions of high temperature (the working condition reaches more than 1000 ℃), strong corrosion (atmosphere containing chlorine and sulfur in the working condition environment) and strong oxidation (higher oxygen content in the working condition environment), so that the problems of high-temperature oxidation and hot corrosion of the nickel-based alloy in the using process are very serious.

In summary, a need exists in the art for a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace and a preparation method thereof, which solve a series of problems of high-temperature oxidation, hot corrosion and the like in the actual use process of nickel-based alloys.

Disclosure of Invention

The invention aims to solve the technical problem that the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace has excellent oxidation resistance and high-temperature resistance.

Meanwhile, the invention provides a preparation method of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace.

Meanwhile, the invention provides an application of the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace in nickel-based alloys for aerospace.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace comprises the following element components in percentage by mass:

。

the microstructure of the material consists of ultrafine net Ti₄Ni₄Si₇And (4) wrapping the intermediate phase.

The crystal grains contain Ti oxide and Si oxide.

A preparation method of a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace comprises the following steps:

s1, proportioning and weighing the components according to the proportion, and then cleaning and drying the components;

s2, placing the dried Ni, Ti, Fe and C in a crucible for vacuum induction smelting, starting magnetic stirring after complete cleaning, and continuing smelting until elements are uniformly distributed to obtain a solution;

s3, adding Si and Al into the uniformly smelted melt, continuing smelting and heating until the melt is completely cleared for the second time, and then stopping heating to obtain an alloy melt;

s4, pouring the smelted alloy melt into a nitrogen-filled air pressure casting heat preservation furnace for heat preservation;

s5, casting the molten steel in the heat preservation furnace into a liquid die forging machine die for liquid die forging, and demolding the alloy material after forging;

s6, placing the demolded alloy material in a vacuum heat treatment furnace for performance heat treatment, and then obtaining the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace.

In S2, the smelting temperature is 1950-2000 ℃, the smelting time is 35-55 min, and the stirring time is 15-30 min.

In S3, the smelting temperature is 1950-2000 ℃, and the smelting time is 25-40 min.

And in S4, the heat preservation temperature is 1750-1800 ℃, and the heat preservation time is 15-35 min.

S5, preheating the die to 400-450 ℃ before casting, wherein the die forging temperature is 1650-1680 ℃, the pressurizing speed is 70-140 mm/S, the mold filling time is 6-9S, the specific pressure is 210-280 Mpa, the pressure maintaining time is 100-180S, and the demolding temperature is 1200-1250 ℃.

In S6, the performance heat treatment is divided into three steps of solid solution, high temperature aging and low temperature aging:

s01: solid solution: preserving the temperature for 5-8 h at 1420-1480 ℃, and then air-cooling to room temperature;

s02: high-temperature aging: preserving heat for 15-19 h at 1200-1250 ℃, and then cooling to room temperature at a cooling rate of 15-23 ℃/s;

s03: low-temperature aging: keeping the temperature of 630-680 ℃ for 20-24 h, and then cooling to room temperature at a cooling rate of 6-9 ℃/s.

An application of a high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace in nickel-based alloys for aerospace.

The invention has the following beneficial effects:

1. oxidation resistance: the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace has a special microstructure, namely the outer layer of crystal grains is wrapped by a superfine three-dimensional reticular mesophase layer. Ti₄Ni₄Si₇The material belongs to a high-density tissue, and on one hand, the material can effectively prevent oxygen from diffusing into the material to generate oxidation. On the other hand, active elements Ti and Si in the phase can take a small amount of diffused oxygen to form stably combined oxide, so that the material has very excellent oxidation resistance.

2. High temperature resistance: the high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace has a special microstructure, namely the outer layer of crystal grains is formed by superfine three-dimensional net-shaped Ti₄Ni₄Si₇And (5) coating the intermediate phase layer. Ti₄Ni₄Si₇The combination of the phases contains stronger covalent bonds, so that the tissue has the characteristics of high melting point, high hardness, high strength, low evaporation rate, low thermal expansion coefficient and the like, thereby showing excellent high temperature resistance.

3. The special component design and preparation process comprises the following steps: three-dimensional network Ti formed in the invention₄Ni₄Si₇The intermediate phase belongs to a thermodynamic metastable product, and the formation of the intermediate phase needs to be performed under the combined action of multiple environmental conditions of high temperature, high pressure and specific cooling rate while the specific component proportion is realized, so that the stable intermediate phase is formed.

Drawings

FIG. 1 is a microstructure of a nickel-base alloy material according to the present invention;

FIG. 2 shows Ti of the present invention₄Ni₄Si₇Phase microstructure and energy spectrum test chart;

FIG. 3 shows Ti of the present invention₄Ni₄Si₇Microstructure and energy spectrum test of granular structure (crystal grains) in the intermediate phase.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.

Example 1:

the high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace comprises the following element components in percentage by mass: si: 13.5 percent; fe: 1.5 percent; ti: 10.3 percent; c: 0.1 percent; al: 2.2 percent; ni: and (4) the balance.

The crystal grains of the microstructure of the material consist of ultrafine net-shaped Ti₄Ni₄Si₇And (4) wrapping the intermediate phase.

The crystal grains contain Ti oxide and Si oxide.

A preparation method of a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace comprises the following steps:

s1, weighing the components according to the proportion, and then cleaning and drying the components;

s2, placing the dried Ni, Ti, Fe and C in a crucible for vacuum induction melting, starting magnetic stirring after complete cleaning, and continuing melting until the elements are uniformly distributed;

s3, adding Si and Al into the uniformly smelted solution, continuing heating until the solution is completely cleared for the second time, and then stopping heating;

s4, pouring the smelted alloy melt into a nitrogen-filled air pressure casting heat preservation furnace for heat preservation;

s5, casting the molten steel in the heat preservation furnace into a liquid die forging machine die for liquid die forging, and demoulding the alloy material after forging;

and S6, placing the demolded alloy material in a vacuum heat treatment furnace for performance heat treatment, and then obtaining the high-temperature-resistant and oxidation-resistant nickel-based alloy material.

In S2, the smelting temperature is 1950 ℃, the smelting time is 35min, and the stirring time is 15 min.

In S3, the smelting temperature is 1950 ℃, and the smelting time is 25 min.

And (5) in S4, keeping the temperature at 1750 ℃ for 15 min.

In S5, the mould is preheated to 400 ℃ before casting, the die forging temperature is 1650 ℃, the pressing speed is 70mm/S, the mold filling time is 6S, the specific pressure is 210Mpa, the pressure maintaining time is 100S, and the demoulding temperature is 1200 ℃.

The performance heat treatment of S6 is divided into three steps of solid solution, high temperature aging and low temperature aging:

s01: solid solution: preserving the temperature for 5 hours at 1420 ℃, and then cooling to room temperature by air;

s02: high-temperature aging: keeping the temperature at 1200 ℃ for 15h, and then cooling to room temperature at a cooling rate of 15 ℃/s;

s03: low-temperature aging: the temperature is kept at 630 ℃ for 20h, and then the temperature is cooled to room temperature at a cooling rate of 6 ℃/s.

Example 2

The high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace comprises the following element components in percentage by mass: si: 15.4 percent; fe: 3.9 percent; ti: 16.7 percent; c: 0.4 percent; al: 5.8 percent; ni: and (4) the balance.

The crystal grains of the microstructure of the material consist of ultrafine net-shaped Ti₄Ni₄Si₇And (4) wrapping the intermediate phase.

The crystal grains contain Ti oxide and Si oxide.

A preparation method of a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace comprises the following steps:

s1, weighing the components according to the proportion, and then cleaning and drying the components;

s2, placing the dried Ni, Ti, Fe and C in a crucible for vacuum induction melting, starting magnetic stirring after complete cleaning, and continuing melting until the elements are uniformly distributed;

s3, adding Si and Al into the uniformly smelted solution, continuing heating until the solution is completely cleared for the second time, and then stopping heating;

s4, pouring the smelted alloy melt into a nitrogen-filled air pressure casting heat preservation furnace for heat preservation;

s5, casting the molten steel in the heat preservation furnace into a liquid die forging machine die for liquid die forging, and demoulding the alloy material after forging;

and S6, placing the demolded alloy material in a vacuum heat treatment furnace for performance heat treatment, and then obtaining the high-temperature-resistant and oxidation-resistant nickel-based alloy material.

In S2, the smelting temperature is 2000 ℃, the smelting time is 55min, and the stirring time is 30 min.

The smelting temperature in S3 is 2000 ℃, and the smelting time is 40 min.

And the heat preservation temperature in S4 is 1800 ℃, and the heat preservation time is 35 min.

S5, before casting, the die is preheated to 450 ℃, the die forging temperature is 1680 ℃, the pressurizing speed is 140mm/S, the mold filling time is 9S, the specific pressure is 280Mpa, the pressure maintaining time is 180S, and the demolding temperature is 1250 ℃.

The performance heat treatment of S6 is divided into three steps of solid solution, high temperature aging and low temperature aging:

s01: solid solution: keeping the temperature at 1480 ℃ for 8h, and then cooling to room temperature in air;

s02: high-temperature aging: keeping the temperature at 1250 ℃ for 19h, and then cooling to room temperature at a cooling rate of 23 ℃/s;

s03: low-temperature aging: the 680 ℃ was incubated for 24h and then cooled to room temperature at a cooling rate of 9 ℃/s.

Example 3

The high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace comprises the following element components in percentage by mass: si: 14.5 percent; fe: 2.5 percent; ti: 13.2 percent; c: 0.3 percent; al: 3.5 percent; ni: and (4) the balance.

The crystal grains of the microstructure of the material consist of ultrafine net-shaped Ti₄Ni₄Si₇And (4) wrapping the intermediate phase.

The crystal grains contain Ti oxide and Si oxide.

A preparation method of a high-temperature-resistant and oxidation-resistant nickel-based alloy material for aerospace comprises the following steps:

s1, weighing the components according to the proportion, and then cleaning and drying the components;

s2, placing the dried Ni, Ti, Fe and C in a crucible for vacuum induction melting, starting magnetic stirring after complete cleaning, and continuing melting until the elements are uniformly distributed;

s3, adding Si and Al into the uniformly smelted solution, continuing heating until the solution is completely cleared for the second time, and then stopping heating;

s4, pouring the smelted alloy melt into a nitrogen-filled air pressure casting heat preservation furnace for heat preservation;

s5, casting the molten steel in the heat preservation furnace into a liquid die forging machine die for liquid die forging, and demoulding the alloy material after forging;

and S6, placing the demolded alloy material in a vacuum heat treatment furnace for performance heat treatment, and then obtaining the high-temperature-resistant and oxidation-resistant nickel-based alloy material.

In S2, the smelting temperature is 1980 ℃, the smelting time is 45min, and the stirring time is 22 min.

In S3, the melting temperature is 1980 ℃, and the melting time is 31 min.

And (5) in S4, keeping the temperature at 1775 ℃ for 25 min.

S5, before casting, the die is preheated to 425 ℃, the die forging temperature is 1665 ℃, the pressing speed is 100mm/S, the mold filling time is 7.5S, the specific pressure is 250Mpa, the pressure maintaining time is 150S, and the demolding temperature is 1225 ℃.

The performance heat treatment of S6 is divided into three steps of solid solution, high temperature aging and low temperature aging:

s01: solid solution: preserving the temperature at 1450 ℃ for 5-8 h, and then cooling to room temperature in air;

s02: high-temperature aging: keeping the temperature at 1225 ℃ for 17h, and then cooling to room temperature at a cooling rate of 20 ℃/s;

s03: low-temperature aging: the temperature is kept at 650 ℃ for 22h, and then the temperature is cooled to room temperature at a cooling rate of 7 ℃/s.

Comparative example 1

A conventional nickel-based alloy (the nickel-based alloy is designated In 738).

The materials of examples 1-3 and comparative example 1 were individually tested for performance, and the results are shown in Table 1.

TABLE 1 Performance data Table

As shown in FIG. 1, a microstructure of the high temperature and oxidation resistant nickel-based alloy material for aerospace obtained in example 1 of the present invention is shown, and Ti is shown in FIG. 1₄Ni₄Si₇The phase structure is a superfine three-dimensional net shape, and crystal grains are wrapped in the phase structure.

As shown in FIG. 2, isTi of high-temperature-resistant oxidation-resistant nickel-based alloy material for aerospace obtained in embodiment 1 of the invention₄Ni₄Si₇Microstructure and energy spectrum test of the mesophase, as can be seen from FIG. 2, for Ti₄Ni₄Si₇Energy spectrum test of a selected region (white square box) of the intermediate phase finds that the components of the part of the structure are Ti, Si and Ni, and the atomic percentage of the elements is about Ti to Ni to Si =4 to 7; thus, the phase is determined to be Ti₄Ni₄Si₇And (4) phase(s).

As shown in FIG. 3, Ti is a high temperature and oxidation resistant Ni-based alloy material for aerospace obtained in example 1 of the present invention₄Ni₄Si₇As can be seen from fig. 3, the microstructure and the energy spectrum test chart of the granular structure (i.e., the crystal grains) in the intermediate phase are subjected to a selected area (white square) energy spectrum test, and the components of the granular structure are mainly three elements of O, Si, and Ti, so that the granular structure is determined to be Ti and Si oxide.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.