CN114645161B - High-oxidation-resistance nickel-based alloy block material and preparation method thereof - Google Patents

Abstract

The invention discloses a high-oxidation-resistance nickel-based alloy block material and a preparation method thereof. The material comprises the following elements in percentage by mass: 22.0 to 23.0 percent of chromium, 13.0 to 16.0 percent of tungsten, less than or equal to 4.0 percent of iron, less than or equal to 1.5 percent of molybdenum, 0.5 percent of boron, 1 percent of silicon, 0.5 to 1 percent of aluminum, 0.3 to 0.7 percent of titanium, less than or equal to 0.5 percent of manganese, less than or equal to 0.1 percent of carbon, less than or equal to 0.13 percent of other impurities and the balance of nickel. The novel high-oxidation-resistance nickel-based alloy block material is designed mainly through regulation and control of elements in the GH3044 alloy and regulation and control of process parameters (pressure, refining temperature and the like) in the preparation process, and compared with the GH3044 alloy, the novel high-oxidation-resistance nickel-based alloy block material is good in deoxidation capability and better in high-temperature oxidation resistance, and the strength of the novel high-oxidation-resistance nickel-based alloy block material is not lower than 85% of that of the GH3044 alloy material, and the hardness of the novel high-oxidation-resistance nickel-based alloy block material is not lower than 90% of that of the GH3044 alloy material.

Description

A kind of highly oxidation-resistant nickel-based alloy bulk material and its preparation method

technical field

The invention relates to the technical field of alloy materials, in particular to a nickel-based alloy bulk material with high oxidation resistance and a preparation method thereof.

Background technique

In an aero-engine, the turbine blade is listed as the first critical part because it is the part with the highest temperature, the most complex stress and the harshest environment. The performance level of the turbine blades has become an important symbol of the advanced level of a type of engine.

A certain type of aero-engine turbine blade is made of high-temperature nickel-based alloy GH3044, and its working temperature is about 850°C. After a certain flight cycle, due to the poor oxidation resistance of GH3044 alloy at high temperature, the blade will wear or crack during work. , Part of the surface is peeled off, which leads to a great decline in its performance, so that it gradually loses its usability, and it must be repaired to restore normal use. Therefore, it is very important to design an alloy material with high oxidation resistance suitable for such aeroengine blades.

Contents of the invention

The object of the present invention is to propose a nickel-based alloy bulk material with high oxidation resistance and a preparation method thereof, aiming at the above-mentioned deficiencies of the prior art.

A high-oxidation-resistant nickel-based alloy bulk material according to the present invention, the mass percentage content of each element in the high-oxidation-resistant nickel-based alloy bulk material is: chromium 22.0%-23.0%, tungsten 13.0%-16.0% , iron ≤ 4.0%, molybdenum ≤ 1.5%, boron 0.5%, silicon 1%, aluminum 0.5% ~ 1%, titanium 0.3% ~ 0.7%, manganese ≤ 0.5%, carbon ≤ 0.1%, other impurities ≤ 0.13%, nickel balance.

Further, the mass percentage content of each element is: chromium 22.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, silicon 1%, aluminum 0.5%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1% , impurity content 0.13%, nickel balance.

Further, the mass percentage content of each element is: chromium 22.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, silicon 1%, aluminum 1%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1% , impurity content 0.13%, nickel balance.

Further, the mass percentage content of each element is: chromium 23.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, silicon 1%, aluminum 0.5%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1% , impurity content 0.13%, nickel balance.

Further, the mass percentage content of each element is: chromium 23.0%, tungsten 15.0%, iron 2.0%, molybdenum 1%, silicon 1%, aluminum 0.5%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1% , impurity content 0.13%, nickel balance.

A method for preparing the above-mentioned high oxidation resistance nickel-based alloy bulk material, comprising the steps of:

S1: Put pure nickel, pure iron, pure graphite, pure chromium, pure tungsten, pure molybdenum, and nickel-boron intermediate alloy into the crucible according to the mass percentage content requirements of each element, vacuumize to 8-12Pa and start heating, after all are melted, Keep the temperature at 1500-1650°C for refining, and the refining time is 20 minutes;

S2: After refining, fill with 0.06-0.08MPa argon gas, add a certain amount of pure titanium, pure manganese, pure aluminum, pure silicon, and prepare for the second melting of raw materials;

S3: After the secondary raw material is completely melted, adjust the temperature for casting, and the casting temperature is 1500-1600°C;

S4: Pour the uniformly melted molten metal into a mold to cool and form a nickel-based alloy block material with high oxidation resistance.

This patent mainly designs a new type of high oxidation resistance nickel-based alloy bulk material through the regulation of the elements in the GH3044 alloy and the regulation of the process parameters (pressure, refining temperature, etc.) in the preparation process. Compared with the GH3044 alloy, it aims to It has good deoxidation ability, better high-temperature oxidation resistance, and guarantees that its strength is not lower than 85% of the strength of the GH3044 alloy material, and its hardness is not lower than 90% of the hardness of the GH3044 alloy material.

Using the above-mentioned element content ratio, compared with the existing alloy material (GH3044 alloy), the high oxidation resistance nickel-based alloy bulk material of this invention has the following advantages: 0.5% boron element is added, and the content of silicon element Increased from 0.8% to 1%, boron and silicon can form a low-melting eutectic compound with manganese, so that boron and silicon can cooperate to play a good deoxidation ability; the content of aluminum increases from 0.5 to 1%, The content of chromium element dropped from 24% to 22% and 23%, because the oxidized material of the original GH3044 powder is mainly NiO, Cr ₂ O ₃ , Al ₂ O ₃ , etc., and the Cr ₂ O ₃ oxide film is non-protective Therefore, the content of chromium element is appropriately reduced, so that the non-protective oxide film Cr ₂ O ₃ produced after oxidation of GH3044 is reduced, and the number of protective oxide films such as Al ₂ O ₃ is increased, thereby improving oxidation resistance and enhancing Surface resistance to peeling. Under the premise of ensuring that its strength is not lower than 85% of the strength of the GH3044 alloy material and its hardness is not lower than 90% of the hardness of the GH3044 alloy material, the high temperature oxidation resistance of the alloy can be enhanced.

Description of drawings

Fig. 1 is the XRD phase analysis diffraction pattern before and after oxidation of the alloy block material in Example 1 of the present invention;

Fig. 2 is the surface morphology diagram of the alloy bulk material after oxidation in Example 1 of the present invention;

3 is an XRD phase analysis diffraction pattern before and after oxidation of the alloy bulk material in Example 2 of the present invention;

Fig. 4 is the surface morphology diagram of the alloy bulk material after oxidation in Example 2 of the present invention;

Fig. 5 is the XRD phase analysis diffraction pattern before and after oxidation of the alloy bulk material in Example 3 of the present invention;

Fig. 6 is the surface morphology diagram of the alloy bulk material after oxidation in Example 3 of the present invention;

Fig. 7 is the XRD phase analysis diffraction pattern before and after oxidation of the alloy bulk material in comparative example 1 of the present invention;

Fig. 8 is the surface morphology diagram of the alloy bulk material after oxidation in Comparative Example 1 of the present invention;

Fig. 9 is an XRD phase analysis diffraction pattern before and after oxidation of the alloy bulk material in Comparative Example 2 of the present invention;

Fig. 10 is a surface morphology diagram of the alloy bulk material in Comparative Example 2 of the present invention after oxidation.

Detailed ways

The following are specific embodiments of the present invention and in conjunction with the accompanying drawings, the technical solutions of the present invention are further described, but the present invention is not limited to these embodiments.

Example 1

Develop a new type of high-temperature nickel-based alloy bulk material according to the mass fraction ratio of the following elements, nickel balance, 22.0% chromium, 15.0% tungsten, 4.0% iron, 1.5% molybdenum, 1% silicon, 0.5% aluminum, and 0.6% titanium %, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13% (phosphorus 0.01%, sulfur 0.01%, copper 0.07%, oxygen 0.02%, nitrogen 0.02%), the sum of each raw material percentage is 100%.

Preparation of raw materials according to the target composition. Put pure nickel, pure iron, pure graphite, pure chromium, pure tungsten, pure molybdenum, and nickel-boron intermediate alloy into the crucible, and pure titanium, pure manganese, pure aluminum, and pure silicon into the secondary feeding bin. Vacuum to 10Pa and start heating. After all the raw materials in the crucible are melted, keep the temperature at 1550°C for refining, and the refining time is 20 minutes. After refining, fill with 0.08MPa argon, add pure titanium, pure manganese, pure aluminum, pure silicon, and prepare for the second melting of raw materials. After the secondary raw material is completely melted, adjust the temperature for casting, the casting temperature is 1570°C, and pour the evenly melted molten metal into the mold for cooling and forming.

Figure 1 is the XRD phase analysis diffraction pattern of the alloy bulk material in Example 1 before and after oxidation, and it can be obtained that the main product after oxidation is Cr _1.3 Fe _0.7 O ₃ , and the main peak is relatively strong; Figure 2 is the alloy bulk material in Example 1 The surface topography after oxidation shows that there is no obvious peeling off the surface. After tensile test at room temperature, it can be obtained that the tensile strength is 708MPa; the hardness at room temperature is 289HV; it is oxidized at a high temperature of 900 degrees Celsius and kept for 100 hours, and the weight gain after oxidation for 100 hours can be obtained by weighing 23.17g/mm ³ . Compared with Comparative Example 1, the oxidation resistance increased by 16.26%.

Example 2

Develop a new type of high-temperature nickel-based alloy bulk material according to the mass fraction ratio of the following elements, nickel balance, chromium 22.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, silicon 1%, aluminum 1%, titanium 0.6 %, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13% (phosphorus 0.01%, sulfur 0.01%, copper 0.07%, oxygen 0.02%, nitrogen 0.02%), the sum of each raw material percentage is 100%.

Preparation of raw materials according to the target composition. Put pure nickel, pure iron, pure graphite, pure chromium, pure tungsten, pure molybdenum, and nickel-boron intermediate alloy into the crucible, and pure titanium, pure manganese, pure aluminum, and pure silicon into the secondary feeding bin. Vacuum to 10Pa and start heating. After all the raw materials in the crucible are melted, keep the temperature at 1550°C for refining, and the refining time is 20 minutes. After refining, fill with 0.08MPa argon, add pure titanium, pure manganese, pure aluminum, pure silicon, and prepare for the second melting of raw materials. After the secondary raw material is completely melted, adjust the temperature for casting, the casting temperature is 1570°C, and pour the evenly melted molten metal into the mold for cooling and forming.

Figure 3 is the XRD phase analysis diffraction pattern of the alloy bulk material in Example 2 before and after oxidation, and it can be obtained that the main product after oxidation is Cr _1.3 Fe _0.7 O ₃ , and the main peak is strong; Figure 4 is the alloy bulk material in Example 2 The surface topography after oxidation shows that there is no obvious peeling off the surface. After tensile test at room temperature, the tensile strength is 789MPa; the hardness at room temperature is 351HV; it is oxidized at a high temperature of 900 degrees Celsius and kept for 100 hours, and the weight gain after 100 hours of oxidation can reach 24.33g/ ^mm3 by weighing , compared with Comparative Example 1, the oxidation resistance increased by 12.07%.

Example 3

Develop a new type of high-temperature nickel-based alloy bulk material according to the mass fraction ratio of the following elements, nickel balance, 23.0% chromium, 15.0% tungsten, 4.0% iron, 1.5% molybdenum, 1% silicon, 0.5% aluminum, and 0.6% titanium %, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13% (phosphorus 0.01%, sulfur 0.01%, copper 0.07%, oxygen 0.02%, nitrogen 0.02%), the sum of each raw material percentage is 100%.

Preparation of raw materials according to the target composition. Put pure nickel, pure iron, pure graphite, pure chromium, pure tungsten, pure molybdenum, and nickel-boron intermediate alloy into the crucible, and pure titanium, pure manganese, pure aluminum, and pure silicon into the secondary feeding bin. Vacuum to 10Pa and start heating. After all the raw materials in the crucible are melted, keep the temperature at 1550°C for refining, and the refining time is 20 minutes. After refining, fill with 0.08MPa argon, add pure titanium, pure manganese, pure aluminum, pure silicon, and prepare for the second melting of raw materials. After the secondary raw material is completely melted, adjust the temperature for casting, the casting temperature is 1570°C, and pour the evenly melted molten metal into the mold for cooling and forming.

Figure 5 is the XRD phase analysis diffraction pattern of the alloy bulk material in Example 3 before and after oxidation, and it can be obtained that the main product after oxidation is Cr _1.3 Fe _0.7 O ₃ , and the main peak is strong; Figure 6 is the alloy bulk material in Example 3 The surface topography after oxidation shows that there is no obvious peeling off the surface. After tensile test at room temperature, the tensile strength is 715MPa; the hardness at room temperature is 299HV; it is oxidized at 900 degrees Celsius and kept for 100 hours, and the weight gain after 100 hours of oxidation can reach 25.83g/ ^mm3 by weighing , compared with Comparative Example 1, the oxidation resistance increased by 6.65%.

Example 4

Develop a new type of high-temperature nickel-based alloy bulk material according to the mass fraction ratio of the following elements, nickel balance, 23.0% chromium, 15.0% tungsten, 2.0% iron, 1% molybdenum, 1% silicon, 0.5% aluminum, and 0.6% titanium %, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13% (phosphorus 0.01%, sulfur 0.01%, copper 0.07%, oxygen 0.02%, nitrogen 0.02%), the sum of each raw material percentage is 100%.

Preparation of raw materials according to the target composition. Put pure nickel, pure iron, pure graphite, pure chromium, pure tungsten, pure molybdenum, and nickel-boron intermediate alloy into the crucible, and pure titanium, pure manganese, pure aluminum, and pure silicon into the secondary feeding bin. Vacuum to 10Pa and start heating. After all the raw materials in the crucible are melted, keep the temperature at 1550°C for refining, and the refining time is 20 minutes. After refining, fill with 0.08MPa argon, add pure titanium, pure manganese, pure aluminum, pure silicon, and prepare for the second melting of raw materials. After the secondary raw material is completely melted, adjust the temperature for casting, the casting temperature is 1570°C, and pour the evenly melted molten metal into the mold for cooling and forming.

After tensile test at room temperature, the tensile strength is 700MPa; the hardness at room temperature is 280HV; it is oxidized at a high temperature of 900 degrees Celsius and kept for 100 hours, and the weight gain after 100 hours of oxidation can reach 25.32g/ ^mm3 by weighing , Compared with Comparative Example 1, the oxidation resistance increased by 8.5%.

Comparative example 1

Develop a kind of high-temperature nickel-base alloy block material with mass fraction ratio according to the following elements as a comparison sample (GH3044 alloy), nickel surplus, chromium 24.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, silicon 0.8%, Aluminum 0.5%, titanium 0.6%, manganese 0.5%, carbon 0.1%, impurity content 0.13% (phosphorus 0.01%, sulfur 0.01%, copper 0.07%, oxygen 0.02%, nitrogen 0.02%), the sum of the percentages of each raw material is 100% .

Figure 7 is the XRD phase analysis diffraction pattern of the alloy bulk material in Comparative Example 1 before and after oxidation. It can be obtained that the main product after oxidation is Cr ₂ O ₃ , but the main peak intensity is not high; Figure 8 is the oxidation of the alloy bulk material in Comparative Example 1. After the surface topography, it was found that the surface was slightly peeled off. After tensile test at room temperature, the tensile strength is 507MPa; the hardness at room temperature is 194HV; it is oxidized at a high temperature of 900 degrees Celsius and kept for 100 hours, and the oxidation weight gain after oxidation for 100 hours is 27.67g/ ^mm3 by weighing .

Comparative example 2

Develop a kind of high-temperature nickel-based alloy block material with the mass fraction ratio of the following elements as a comparison sample, nickel surplus, 22.0% chromium, 15.0% tungsten, 4.0% iron, 1.5% molybdenum, 1% silicon, 0.5% aluminum, Titanium 0.6%, manganese 0.5%, boron 1.5%, carbon 0.1%, impurity content 0.13% (phosphorus 0.01%, sulfur 0.01%, copper 0.07%, oxygen 0.02%, nitrogen 0.02%), the sum of the percentages of each raw material is 100% .

Figure 9 is the XRD phase analysis diffraction pattern of the alloy bulk material in Comparative Example 2 before and after oxidation. It can be obtained that the main products after oxidation are (Ni, Fe), Cr _1.3 Fe _0.7 O ₃ , and the phase strength of Cr _1.3 Fe _0.7 O ₃ Not high; the surface is gray-green after oxidation. Figure 10 is the surface morphology of the alloy bulk material in Comparative Example 2 after oxidation. After a tensile test at room temperature, the tensile strength is 536MPa, and it can be seen that the strength is lower than when the boron content is 0.5%. By weighing, it can be obtained that the oxidation weight gain after oxidation for 100 hours is 33 g/mm ³ .

What is not involved above is applicable to the prior art.

Although some specific embodiments of the present invention have been described in detail by examples, those skilled in the art should understand that the above examples are only for illustration, rather than for limiting the scope of the present invention. Various modifications or additions or similar substitutions can be made to the described specific embodiments without departing from the direction of the present invention or exceeding the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent replacements, improvements, etc. made to the above implementations based on the technical essence of the present invention shall be included in the protection scope of the present invention.

Claims (6)

1. A high-oxidation-resistant nickel-based alloy bulk material, characterized in that the mass percentage content of each element of the high-oxidation-resistant nickel-based alloy bulk material is: chromium 22.0% to 23.0%, tungsten 13.0% ～16.0%, iron 2.0%～4.0%, molybdenum 1%～1.5%, boron 0.5%, silicon 1%, aluminum 0.5%～1%, titanium 0.3%～0.7%, manganese 0.5%, carbon 0.1%, other impurities Content ≤ 0.13%, nickel balance. 2. A kind of high oxidation resistance nickel base alloy bulk material according to claim 1, is characterized in that, the mass percentage content of each element is: chromium 22.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, Silicon 1%, aluminum 0.5%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13%, nickel balance. 3. A kind of highly oxidation-resistant nickel-based alloy bulk material according to claim 1, characterized in that, the mass percentage content of each element is: chromium 22.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, Silicon 1%, aluminum 1%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13%, nickel balance. 4. A high oxidation resistance nickel-base alloy bulk material according to claim 1, characterized in that the mass percentage content of each element is: chromium 23.0%, tungsten 15.0%, iron 4.0%, molybdenum 1.5%, Silicon 1%, aluminum 0.5%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13%, nickel balance. 5. A high oxidation resistance nickel-based alloy bulk material according to claim 1, characterized in that the mass percentage content of each element is: chromium 23.0%, tungsten 15.0%, iron 2.0%, molybdenum 1%, Silicon 1%, aluminum 0.5%, titanium 0.6%, manganese 0.5%, boron 0.5%, carbon 0.1%, impurity content 0.13%, nickel balance. 6. A method for preparing the high oxidation resistance nickel-based alloy bulk material as claimed in any one of claims 1-5, characterized in that, comprising the steps of: S1: Put pure nickel, pure iron, pure graphite, pure chromium, pure tungsten, pure molybdenum, and nickel-boron intermediate alloy into the crucible according to the mass percentage content requirements of each element, vacuumize to 8-12Pa and start heating, after all are melted, Keep the temperature at 1500-1650°C for refining, and the refining time is 20 minutes; S2: After refining, fill with 0.06-0.08MPa argon gas, add a certain amount of pure titanium, pure manganese, pure aluminum, pure silicon, and prepare for the second melting of raw materials; S3: After the secondary raw material is completely melted, adjust the temperature for casting, and the casting temperature is 1500-1600°C; S4: Pour the uniformly melted molten metal into a mold to cool and form a nickel-based alloy block material with high oxidation resistance.

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