Rare earth-doped high-temperature-resistant chemical-resistant alloy material and preparation method thereof

Abstract

The invention relates to the technical field of alloys, in particular to a rare earth-doped high-temperature-resistant chemical-resistant alloy material and a preparation method thereof. The material comprises the following components in parts by weight: 2.34 to 4.39 parts of cerium, 1.48 to 1.96 parts of dicerium trioxide, 4.34 to 7.28 parts of europium, 2.24 to 3.54 parts of europium oxide, 1.84 to 2.68 parts of yttrium, 0.58 to 1.03 parts of yttrium oxide, 4.85 to 6.96 parts of titanium, 2.58 to 3.67 parts of titanium dioxide, 5.21 to 8.56 parts of hafnium, 2.56 to 4.32 parts of hafnium dioxide, 10.24 to 20.34 parts of nitrogen-doped tungsten carbide and the balance of nickel. The alloy material provided by the invention has excellent high temperature resistance and chemical resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of alloys, and in particular relates to a rare earth-doped high-temperature-resistant and chemical-resistant alloy material and a preparation method thereof. Background Art

[0002] Nickel-based alloys are a type of alloy that uses nickel as the base element and adds two or more other elements in a certain proportion. They have received widespread attention due to their excellent properties, including excellent resistance to high-temperature oxidation, acid corrosion, and high tensile strength and yield strength. In addition, nickel-based alloys also have strong resistance to localized corrosion, pitting corrosion, and stress corrosion cracking. Its unique combination of properties makes it popular in various industrial applications. In order to meet specific usage requirements, a variety of nickel-based alloys have been developed and commercialized, such as Hastelloy, Inconel, Monel, and Incoloy series, which are widely used in aerospace, marine, chemical, electronics, medical, and energy industries.

[0003] However, the excellent corrosion resistance of nickel-based alloys mainly comes from the stable and dense passivation film formed on their surface. This passivation film is naturally formed in the presence of oxygen and moisture, and can serve as a barrier to prevent corrosive media from further corroding the substrate. However, in the presence of strong acids and alkalis, the passivation film of nickel-based alloys is easily destroyed. In addition, its wear resistance is also poor, and the passivation film is also easily damaged by wear.

[0004] For example, CN119061291A discloses a corrosion-resistant nickel alloy and its preparation method and application, wherein the composition includes: Ni: 52-56wt%, Mo: 2-4wt%, Mn: 0.9-1.1wt%, Ce: 0.5-1.0wt%; Sm: 0.5-1.0wt%, Ca: 0.2-0.4wt%, and the balance is copper. The nickel alloy of the present application improves the corrosion resistance of the nickel alloy by adding modified metals Mo, Mn, Ce, Sm and Ca during the preparation process, but the solubility of the rare earth elements added in the application in the nickel-based alloy is limited. During the solidification process, the rare earth elements are very likely to segregate and are enriched in certain local areas, making it difficult to achieve uniform distribution. This component segregation will cause huge performance differences in different parts of the alloy. The area with a high rare earth content may have poor mechanical properties due to excessive brittle phases; while the area lacking rare earth elements cannot obtain the expected performance improvement effect.

[0005] For example, CN114318107A discloses a corrosion-resistant nickel alloy and its preparation method and application. The alloy includes the following components by mass: B 4.68-5.35%, W 5.69-6.41%, Cr 27.68-28.39%, Al 12.65-13.42%, and the rest is Ni and inevitable impurities. The alloy of the present invention is a Ni‑W‑B ternary alloy, the main components of which are Ni, W, and B. These three elements have strong high-temperature corrosion resistance at around 600°C, and are all solid solution forming elements, with the potential for solid solution hardening and precipitation formation, thereby improving the creep strength of the nickel alloy matrix. This application forms Al 2 O 3 and Cr 2 O 3 The oxide layer acts as a physical diffusion barrier to corrosive gases such as chlorine, but the wear resistance of the alloy still needs to be improved.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The object of the present invention is to provide a rare earth-doped high-temperature resistant and chemical-resistant alloy material and a preparation method thereof. The alloy material provided by the present invention has excellent high-temperature resistance and chemical resistance.

[0008] In order to achieve the above object, the present invention provides the following technical solutions: In the first aspect, an embodiment of the present invention provides a rare earth-doped high-temperature and chemical-resistant alloy material, comprising the following components in parts by weight: 2.34-4.39 parts of cerium, 1.48-1.96 parts of cerium trioxide, 4.34-7.28 parts of europium trioxide, 2.24-3.54 parts of europium trioxide, 1.84-2.68 parts of yttrium, 0.58-1.03 parts of yttrium trioxide, 4.85-6.96 parts of titanium, 2.58-3.67 parts of titanium dioxide, 5.21-8.56 parts of hafnium, 2.56-4.32 parts of hafnium dioxide, 10.24-20.34 parts of nitrogen-doped tungsten carbide, and the balance is nickel.

[0009] In a preferred embodiment, the alloy material includes the following components by weight: 2.5-4.0 parts of cerium, 1.6-1.8 parts of cerium trioxide, 4.5-7.0 parts of europium, 2.5-3.0 parts of europium trioxide, 1.9-2.2 parts of yttrium, 0.8-1.0 parts of yttrium trioxide, 5.0-6.5 parts of titanium, 2.8-3.5 parts of titanium dioxide, 5.5-8.0 parts of hafnium, 2.8-4.0 parts of hafnium dioxide, 12-18 parts of nitrogen-doped tungsten carbide, and the balance is nickel.

[0010] In the present invention, the high temperature resistance and chemical resistance of the alloy material are effectively improved by compounding metal elements, rare earth elements and corresponding oxides. This is mainly because when simply adding metal elements to improve corrosion resistance through the formation of their oxides, the corresponding oxide particles will adhere to the surface of the metal particles, resulting in weakened grain refinement and mechanical properties, resulting in poor corresponding performance. The oxide dispersion strengthening of the present invention effectively hinders dislocation movement and further improves the high temperature resistance and chemical resistance of the alloy material.

[0011] Specifically, cerium in nickel-based alloys is easily oxidized at high temperatures to form cerium oxide, which can preferentially react with oxygen in the environment to build a protective barrier on the alloy surface, slowing down the oxidation rate of the nickel matrix and improving the alloy's antioxidant capacity, allowing the nickel-based alloy to maintain stable performance in a high-temperature oxidizing environment. When the nickel alloy solidifies, the cerium element can act as a heterogeneous nucleation core, increasing the number of crystal nuclei and refining the grains, thereby enhancing the strength and toughness of the alloy. The added cerium trioxide can partially decompose during the alloy smelting and sintering process, releasing cerium atoms that merge into the nickel matrix, playing a similar antioxidant and grain-refining effect as cerium alone; the remaining cerium trioxide particles can also act as a dispersed phase to hinder dislocation movement and improve the strength of the alloy.

[0012] The incorporation of europium into nickel-based alloys can optimize the electronic structure of the alloys. The presence of europium may enhance the magnetism of nickel alloys. At the same time, some europium will also be enriched on the surface of the alloys and react with oxygen, protecting the alloys from corrosion to a certain extent and improving corrosion resistance. When europium trioxide comes into contact with nickel at high temperatures, on the one hand, it decomposes to produce europium atoms to change the properties of the alloy matrix; on the other hand, the undecomposed part acts as a second phase, changing the internal stress distribution of the alloy and cooperating with the nickel matrix to improve the high-temperature creep resistance of the alloy.

[0013] Yttrium is added to nickel-based alloys and combines with oxygen at high temperatures to form stable yttrium trioxide, which supplements and stabilizes the oxide film on the surface of the alloy, greatly enhancing the anti-oxidation and anti-sulfurization properties of the nickel alloy. Yttrium also tends to segregate at grain boundaries, hindering grain boundary migration, preventing abnormal grain growth, maintaining a fine grain state, and improving the strength and toughness of nickel alloys. In addition, yttrium trioxide is evenly distributed in the nickel matrix as a dispersed phase, hindering dislocation slip and playing a precipitation strengthening role; it can also absorb impurity elements in the alloy, purify the alloy, and improve the comprehensive mechanical properties of the alloy.

[0014] Titanium and nickel can form an intermetallic compound, nickel titanate, which acts as a strengthening phase and is distributed in the nickel matrix, significantly improving the strength and hardness of the alloy while maintaining a certain toughness. In addition, the addition of an appropriate amount of titanium changes the crystal structure and phase composition of the nickel alloy, reduces the alloy's work hardening rate, and makes the nickel alloy easier to form during hot and cold processing. In addition, when sintering and smelting nickel-based alloys, part of the titanium dioxide will be reduced, releasing titanium atoms to participate in the alloying reaction; the remaining titanium dioxide particles are evenly dispersed, which has a dispersion strengthening effect and improves the strength of the alloy; and nickel titanate can also adsorb inclusions in the alloy to a certain extent and purify the alloy structure.

[0015] After hafnium is incorporated into the nickel-based alloy, intermetallic compounds such as nickel hafniumide and nickel hafniumide are formed at high temperatures. These compounds precipitate and improve the strength and creep resistance of the nickel alloy in high-temperature environments, helping the alloy to serve for a long time at high temperatures. In addition, the addition of hafnium adjusts the passivation film composition of the nickel alloy, increases the proportion of corrosion-resistant components such as cerium trioxide, and enhances the corrosion resistance of the alloy in corrosive media. In addition, hafnium dioxide is dispersed in the nickel alloy as a hard point, hindering dislocation movement and achieving dispersion strengthening; at the same time, it has a high melting point and chemical stability, which can improve the overall high temperature resistance and wear resistance of the alloy, allowing the nickel alloy to adapt to more severe working conditions.

[0016] It should also be noted that rare earth oxides such as cerium trioxide, yttrium trioxide and europium trioxide all have good chemical stability. In a high-temperature oxygen environment, they can cooperate with each other to promote the formation of a denser and continuous oxide film. When cerium trioxide and yttrium trioxide exist at the same time, cerium trioxide can quickly capture the initial oxygen atoms, and then yttrium trioxide and europium trioxide participate in stabilizing the film structure and improving the overall oxidation resistance of the material. In addition, the oxides of cerium, europium and yttrium have high chemical activity. When smelted at high temperatures, they can work synergistically to react with impurity elements such as sulfur and phosphorus in the alloy to form high-melting point compounds, and together remove impurities from the melt, purify the alloy system, and improve the performance of the final material. Titanium dioxide, hafnium dioxide and rare earth oxides work together to enhance the high-temperature performance of the material. At high temperatures, titanium dioxide and hafnium dioxide can improve the rigidity and hardness of the material, while rare earth oxides are responsible for stabilizing the interface and preventing grain boundary migration, so that the material can withstand greater stress in a high-temperature environment and maintain structural stability.

[0017] In a preferred embodiment, the preparation method of the nitrogen-doped tungsten carbide is as follows: Tungsten trioxide, fructose, melamine, L-cysteine, sodium chloride, potassium chloride and water are mixed and stirred to mix evenly, and then heated until the water is dry to obtain a solid phase. The solid phase is kept warm and reacted in a nitrogen atmosphere, and after cooling, it is washed, dried, ground and sieved to obtain nitrogen-doped tungsten carbide.

[0018] In a preferred embodiment, the mass ratio of tungsten trioxide, fructose, melamine, L-cysteine, sodium chloride, potassium chloride and water is 1:(2-3):(1-2):(0.1-0.5):(10-15):(10-15):(50-100).

[0019] In a preferred embodiment, the heating temperature is 40-80°C.

[0020] In a preferred embodiment, the conditions for the thermal insulation reaction are: temperature 700-1000° C., time 1-5 h.

[0021] In a preferred embodiment, the sieve used for screening is 200-400 mesh.

[0022] The present invention effectively improves the adverse effects of metal oxides and rare earth oxides by adding nitrogen-doped tungsten carbide, and at the same time improves the high temperature resistance and chemical properties of the alloy material. And the dispersibility of tungsten carbide is improved by nitrogen-doping, mainly because nitrogen doping changes the surface electronic structure and chemical activity of tungsten carbide. After the introduction of nitrogen atoms, the surface energy of tungsten carbide is reduced, so that the wettability between it and the alloy melt is improved. Good wettability is the key prerequisite for achieving uniform dispersion. When tungsten carbide particles are more easily wetted by the alloy melt, the alloy liquid can spread more smoothly on the surface of the particles, reduce agglomeration, and promote the uniform dispersion of particles in the alloy system. Furthermore, the addition of nitrogen can fine-tune the crystal structure of tungsten carbide, which may inhibit the abnormal growth of tungsten carbide grains. Smaller tungsten carbide particles have a larger specific surface area, and the cohesive force between particles is relatively weak, making it easier to disperse in the alloy matrix; moreover, the change in crystal structure brought about by nitrogen doping will also form a more suitable lattice matching relationship between particles and alloys, further facilitating dispersion. It should also be noted that the new nitrogen-containing phase or chemical bond generated by nitrogen doping enhances the interfacial bonding between tungsten carbide and the alloy. During the solidification or thermal processing of the alloy, strong interfacial bonding can prevent the tungsten carbide particles from detaching from the alloy matrix and reaggregating due to external forces, thermal stress and other factors, stabilize the dispersion state, keep the particles evenly distributed, and give full play to the effectiveness of enhancement and modification.

[0023] In terms of improving the adverse effects of metal oxides and rare earth oxides, the added metal oxides may exist in the alloy in the form of inclusions. These inclusions will destroy the matrix continuity of the alloy and become stress concentration points, which are easy to cause the initiation and expansion of cracks when subjected to stress, thereby reducing the mechanical properties of the alloy, especially the toughness and fatigue properties. The addition of nitrogen-doped tungsten carbide can hinder crack propagation, disperse stress concentration, enhance adhesion, coordinate deformation, limit the size of inclusions, and increase grain boundary "buffers" to avoid the above adverse effects. Among them, in terms of hindering crack propagation, nitrogen-doped tungsten carbide has high hardness and high strength, and is evenly distributed in the alloy in the form of fine dispersed particles. When the alloy is stressed and the cracks extend toward the inclusions, the tungsten carbide particles can act like a "barrier", relying on their own strong resistance to hinder and deflect the extension path of the cracks, prevent the cracks from quickly penetrating the entire alloy, and slow down the rate of mechanical properties degradation caused by crack propagation caused by inclusions. In terms of dispersing stress concentration, since tungsten carbide particles are dispersed throughout the alloy matrix, the stress originally concentrated at the metal oxide inclusions will be shared by the tungsten carbide particles. When subjected to stress, stress can be transmitted and dispersed through the interface between the particles and the matrix, reducing the degree of stress concentration and reducing the risk of cracks in the alloy due to excessive local stress. In terms of enhancing adhesion, nitrogen doping changes the surface properties of tungsten carbide, forming a stronger chemical bond or physical adhesion between it and the alloy matrix and metal oxide inclusions. When the alloy is deformed by force, this good interface bonding can ensure that the inclusions are not easy to peel off and separate from the matrix, avoid new voids and stress concentration caused by the debonding of inclusions, and maintain the integrity of the alloy structure. In terms of coordinated deformation, nitrogen-doped tungsten carbide can coordinate the differences in thermal expansion coefficient, elastic modulus, etc. between the alloy matrix and inclusions to a certain extent. When the temperature changes or when subjected to force, the three can deform more synchronously, reducing the internal stress accumulated around the inclusions due to uncoordinated deformation and reducing the probability of crack initiation. In terms of limiting the size of inclusions, nitrogen-doped tungsten carbide can act as a heterogeneous nucleation core during the solidification process of the alloy, promoting grain refinement. While refining the grains, it will limit the growth of metal oxide inclusions, making the size of the inclusions smaller, and reducing the large-area stress concentration and matrix continuity damage caused by large-sized inclusions. In terms of increasing grain boundary "buffers", fine grains bring more grain boundaries. The grain boundaries themselves are obstacles to dislocation movement and can also absorb and buffer stress. Even if stress concentration occurs around the inclusions, the grain boundary network can disperse and eliminate the stress, weakening the negative impact on the toughness and fatigue properties of the alloy.

[0024] However, too many rare earth elements may segregate at the grain boundaries to form coarse rare earth phases. The presence of these phases will weaken the bonding force of the grain boundaries and reduce the mechanical properties of the alloy. Similarly, the addition of nitrogen-doped tungsten carbide improves the above-mentioned adverse effects by hindering phase growth and strengthening the grain boundary structure. In terms of hindering phase growth, nitrogen-doped tungsten carbide exists in the alloy in the form of small and evenly distributed particles, and these particles can play a "pinning" role at the grain boundaries. When rare earth elements tend to segregate at the grain boundaries and form coarse phases, tungsten carbide particles will rely on their own high hardness and stability to hinder the further growth of rare earth phases, limit their coarsening, and avoid the formation of oversized rare earth phases that seriously weaken the grain boundary bonding force. In terms of strengthening the grain boundary structure, tungsten carbide particles have a strong interaction with the grain boundaries, and nitrogen doping improves the stability of this interaction. It can fill some defect sites at the grain boundaries, make the atomic arrangement of the grain boundaries more regular, enhance the ability of the grain boundaries to resist deformation and cracking, compensate for the weakened grain boundary bonding force due to the rare earth phase, and maintain the overall mechanical properties of the alloy.

[0025] In a second aspect, an embodiment of the present invention provides a method for preparing the rare earth-doped high temperature resistant and chemical resistant alloy material as described above, comprising the following steps: Nickel, cerium, cerium trioxide, europium, europium trioxide, yttrium, yttrium trioxide, titanium, titanium dioxide, hafnium, hafnium dioxide and nitrogen-doped tungsten carbide raw materials are added to a ball mill, and after adding ethanol, a mixed slurry is obtained after ball milling. The mixed slurry is then vacuum dried and sintered, and then heat treated and cooled to obtain an alloy material.

[0026] In a preferred embodiment, the ball milling conditions are: ball milling at 500-700 rpm for 48-72 hours.

[0027] In a preferred embodiment, the amount of ethanol added is 1-3wt% of the raw material.

[0028] In a preferred embodiment, the sintering temperature is 800-1000° C., the sintering time is 1-2 hours, and the sintering condition is vacuum.

[0029] In a preferred embodiment, the heat treatment conditions are: in an argon atmosphere, keeping the temperature at 700-900° C. for 24-36 hours.

[0030] Compared with the prior art, the advantages and beneficial effects of the present invention are: 1. In the present invention, the high temperature resistance and chemical resistance of the alloy material are effectively improved by compounding metal elements, rare earth elements and corresponding oxides. This is mainly because when simply adding metal elements to improve corrosion resistance through the formation of their oxides, the corresponding oxide particles will adhere to the surface of the metal particles, resulting in a weakening of the grain refinement effect and mechanical properties, resulting in poor corresponding performance. The oxide dispersion strengthening of the present invention effectively hinders dislocation movement and further improves the high temperature resistance and chemical resistance of the alloy material.

[0031] 2. The present invention effectively improves the adverse effects of metal oxides and rare earth oxides by adding nitrogen-doped tungsten carbide, and at the same time improves the high temperature resistance and chemical properties of the alloy material. And the dispersibility of tungsten carbide is improved by nitrogen-doping, mainly because nitrogen doping changes the surface electronic structure and chemical activity of tungsten carbide. After the introduction of nitrogen atoms, the surface energy of tungsten carbide is reduced, so that the wettability between it and the alloy melt is improved. Good wettability is the key prerequisite for achieving uniform dispersion. When tungsten carbide particles are more easily wetted by the alloy melt, the alloy liquid can spread more smoothly on the surface of the particles, reduce agglomeration, and promote the uniform dispersion of particles in the alloy system. Furthermore, the incorporation of nitrogen can fine-tune the crystal structure of tungsten carbide, which may inhibit the abnormal growth of tungsten carbide grains. Smaller tungsten carbide particles have a larger specific surface area, and the cohesive force between particles is relatively weak, making it easier to disperse in the alloy matrix; moreover, the changes in the crystal structure brought about by nitrogen doping will also form a more suitable lattice matching relationship between the particles and the alloy, further facilitating dispersion. It should also be noted that the new nitrogen-containing phase or chemical bond generated by nitrogen doping enhances the interfacial bonding between tungsten carbide and the alloy. During the solidification or thermal processing of the alloy, strong interfacial bonding can prevent the tungsten carbide particles from detaching from the alloy matrix and reaggregating due to external forces, thermal stress and other factors, stabilize the dispersion state, keep the particles evenly distributed, and give full play to the effectiveness of enhancement and modification. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Unless otherwise specified, the raw materials and reagents used in the present invention are commercially available.

[0034] Example 1 This embodiment provides a method for preparing a rare earth-doped high temperature resistant and chemical resistant alloy material, comprising the following steps: In parts by mass, 52.3 parts of nickel, 3 parts of cerium, 1.6 parts of cerium trioxide, 5 parts of europium, 2.6 parts of europium trioxide, 2 parts of yttrium, 0.8 parts of yttrium trioxide, 5.5 parts of titanium, 3 parts of titanium dioxide, 6 parts of hafnium, 3.2 parts of hafnium dioxide and 15 parts of nitrogen-doped tungsten carbide raw materials are added to a ball mill, after adding ethanol, the amount of ethanol added is 2wt% of the raw materials, then ball milling is carried out at 600rpm for 36h, and then a mixed slurry is obtained. Then the mixed slurry is vacuum dried and sintered. Specifically, it is sintered at 1000°C under vacuum for 1.5h, then kept at 900°C for 30h in an argon atmosphere, and the alloy material is obtained after natural cooling.

[0035] The preparation method of nitrogen-doped tungsten carbide is as follows: By mass, 1 part of tungsten trioxide, 2.2 parts of fructose, 1.3 parts of melamine, 0.2 parts of L-cysteine, 11 parts of sodium chloride, 12 parts of potassium chloride and 70 parts of water were mixed and stirred to mix evenly, and then heated at 60°C until the water was dry to obtain a solid phase. The solid phase was kept at 800°C for 2 hours in a nitrogen atmosphere, cooled, washed, dried, and ground through a 300-mesh sieve to obtain nitrogen-doped tungsten carbide.

[0036] Example 2 This embodiment provides a method for preparing a rare earth-doped high temperature resistant and chemical resistant alloy material, comprising the following steps: In parts by mass, 45.6 parts of nickel, 3.5 parts of cerium, 1.8 parts of cerium trioxide, 6.5 parts of europium, 2.8 parts of europium trioxide, 2.1 parts of yttrium, 0.9 parts of yttrium trioxide, 6 parts of titanium, 3.2 parts of titanium dioxide, 7 parts of hafnium, 3.6 parts of hafnium dioxide and 17 parts of nitrogen-doped tungsten carbide raw materials are added to a ball mill, and after adding ethanol, the amount of ethanol added is 2wt% of the raw materials, followed by ball milling at 600rpm for 36h, and then a mixed slurry is obtained, and then the mixed slurry is vacuum dried and sintered, specifically, sintered at 1000°C under vacuum for 1.5h, then kept at 900°C for 30h in an argon atmosphere, and naturally cooled to obtain an alloy material.

[0037] The preparation method of nitrogen-doped tungsten carbide is as follows: By mass, 1 part of tungsten trioxide, 2.2 parts of fructose, 1.3 parts of melamine, 0.2 parts of L-cysteine, 11 parts of sodium chloride, 12 parts of potassium chloride and 70 parts of water were mixed and stirred to mix evenly, and then heated at 60°C until the water was dry to obtain a solid phase. The solid phase was kept at 800°C for 2 hours in a nitrogen atmosphere, cooled, washed, dried, and ground through a 300-mesh sieve to obtain nitrogen-doped tungsten carbide.

[0038] Comparative Example 1 The difference between this comparative example and Example 1 is that cerium trioxide is not added, and the mass portion of cerium is changed to 4.6 parts.

[0039] Comparative Example 2 The difference between this comparative example and Example 1 is that no europium trioxide is added, and the mass portion of europium is changed to 7.6 parts.

[0040] Comparative Example 3 The difference between this comparative example and Example 1 is that yttrium trioxide is not added, and the mass portion of yttrium is changed to 2.8 parts.

[0041] Comparative Example 4 The difference between this comparative example and Example 1 is that titanium dioxide is not added and the mass fraction of titanium is changed to 8.5 parts.

[0042] Comparative Example 5 The difference between this comparative example and Example 1 is that hafnium dioxide is not added and the mass fraction of hafnium is changed to 9.2 parts.

[0043] Comparative Example 6 The difference between this comparative example and Example 1 is that cerium trioxide, europium trioxide, yttrium trioxide, titanium dioxide and hafnium dioxide are not added, and the mass part of cerium is changed to 4.6 parts, the mass part of europium is changed to 7.6 parts, the mass part of yttrium is changed to 2.8 parts, the mass part of titanium is changed to 8.5 parts, and the mass part of hafnium is changed to 9.2 parts.

[0044] Comparative Example 7 The difference between this comparative example and Example 1 is that no nitrogen-doped tungsten carbide is added, and the mass fraction of nickel is changed to 67.3 parts.

[0045] Comparative Example 8 The difference between this comparative example and Example 1 is that the nitrogen-doped tungsten carbide is replaced with tungsten carbide.

[0046] Performance Testing 1. The tensile strength of the alloy materials obtained in the examples and comparative examples at room temperature 25°C and 600°C was tested with reference to GB / T 228.1-2010. The results are shown in Table 1.

[0047] 2. Use UMT-3 controlled environment friction and wear testing machine to carry out anti-wear test: pressure 100N, speed 300r / min, time 90min, measure the wear amount, the results are shown in Table 1.

[0048] 3. Referring to GB / T 10125-199, the alloy materials obtained in the examples and comparative examples were placed in a salt spray formed by a 5wt% NaCl solution for 8 hours and then placed for 16 hours. The average corrosion rate was measured to examine the corrosion resistance of the alloy. The results are shown in Table 1.

[0049] Table 1 Performance test results

[0050] It can be seen from the above performance test results that the high temperature resistance and corrosion resistance of Examples 1-2 are significantly improved, especially the comprehensive performance of Example 2 is the most outstanding. This is mainly because the synergistic effect between the composite metal oxides, rare earth oxides and nitrogen-doped tungsten carbide of the present invention effectively improves the high temperature resistance and corrosion resistance of the alloy material.

[0051] The comparative example does not adopt the necessary technical solution, resulting in its performance being significantly worse than that of the embodiment in the corresponding performance test. This better proves the irreplaceable nature of the specific technical solution of the present application in achieving technical effects and solving technical problems.

[0052] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A rare earth-doped high temperature resistant and chemical resistant alloy material, characterized in that: The invention comprises the following components in parts by weight: 2.34-4.39 parts of cerium, 1.48-1.96 parts of cerium trioxide, 4.34-7.28 parts of europium, 2.24-3.54 parts of europium trioxide, 1.84-2.68 parts of yttrium, 0.58-1.03 parts of yttrium trioxide, 4.85-6.96 parts of titanium, 2.58-3.67 parts of titanium dioxide, 5.21-8.56 parts of hafnium, 2.56-4.32 parts of hafnium dioxide, 10.24-20.34 parts of nitrogen-doped tungsten carbide, and the balance is nickel.

2. The rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 1, characterized in that: The alloy material includes the following components by weight: 2.5-4.0 parts of cerium, 1.6-1.8 parts of cerium trioxide, 4.5-7.0 parts of europium, 2.5-3.0 parts of europium trioxide, 1.9-2.2 parts of yttrium, 0.8-1.0 parts of yttrium trioxide, 5.0-6.5 parts of titanium, 2.8-3.5 parts of titanium dioxide, 5.5-8.0 parts of hafnium, 2.8-4.0 parts of hafnium dioxide, 12-18 parts of nitrogen-doped tungsten carbide, and the balance is nickel.

3. The rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 1 or 2, characterized in that: The preparation method of the nitrogen-doped tungsten carbide is as follows: Tungsten trioxide, fructose, melamine, L-cysteine, sodium chloride, potassium chloride and water are mixed and stirred to mix evenly, and then heated until the water is dry to obtain a solid phase. The solid phase is kept warm and reacted in a nitrogen atmosphere, and after cooling, it is washed, dried, ground and sieved to obtain nitrogen-doped tungsten carbide.

4. The rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 3, characterized in that: The mass ratio of tungsten trioxide, fructose, melamine, L-cysteine, sodium chloride, potassium chloride and water is 1:(2-3):(1-2):(0.1-0.5):(10-15):(10-15):(50-100).

5. The rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 3, characterized in that: The heating temperature is 40-80°C.

6. The rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 3, characterized in that: The conditions for the heat preservation reaction are: temperature 700-1000° C., time 1-5 h.

7. The rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 3, characterized in that: The sieve used for the screening is 200-400 meshes.

8. A method for preparing a rare earth-doped high temperature resistant and chemical resistant alloy material as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: Nickel, cerium, cerium trioxide, europium, europium trioxide, yttrium, yttrium trioxide, titanium, titanium dioxide, hafnium, hafnium dioxide and nitrogen-doped tungsten carbide raw materials are added to a ball mill, and after adding ethanol, a mixed slurry is obtained after ball milling. The mixed slurry is then vacuum dried and sintered, and then heat treated and cooled to obtain an alloy material.

9. The method for preparing the rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 8, characterized in that: The ball milling conditions are: ball milling at 500-700 rpm for 48-72 hours; And / or, the amount of ethanol added is 1-3wt% of the raw material.

10. The method for preparing the rare earth-doped high temperature resistant and chemical resistant alloy material according to claim 8, characterized in that: The sintering temperature is 800-1000°C, the sintering time is 1-2h, and the sintering condition is vacuum; And / or, the heat treatment condition is: in an argon atmosphere, keeping the temperature at 700-900° C. for 24-36 hours.

Images