阅读说明：本技术 一种高温镍基合金hred6及其制备方法 (High-temperature nickel-based alloy HRED6 and preparation method thereof ) 是由 汤俊波 于 2021-07-13 设计创作，主要内容包括：本发明公开了一种高温镍基合金HRED6及其制备方法,所述高温镍基合金HRED6包括以下重量份的组分：镍48.0～50.0％,铬27.0～30.0％,钨4.0～6.0％,硅1.2～2.0％,铌1.2～1.8％,碳0.40～0.45％,锰0.5～1.5％,钴＜0.5％,氮≤0.05％,磷＜0.035％,硫＜0.03％。本发明通过对镍基合金中的元素组成进行合理优选,并对其制备方法进行优化,制备得到了高温镍基合金HRED6,与现有的镍基合金相比,其高温特性显著提高,在1200℃的高温处理条件下,仍具有优异的拉伸强度、断裂韧性、持久寿命和抗腐蚀等性能,其中拉伸强度≥744MPa,屈服强度≥832MPa,断裂韧性≥42.8MPa·m～(1/2),断裂伸长率≥9.3％,持久寿命≥367h,相对腐蚀率≤41.3％,因此在工装的热处理过程中不易出现变形、开裂等现象,提高了工装的使用寿命,进而提高了生产效率。(The invention discloses a high-temperature nickel-based alloy HRED6 and a preparation method thereof, wherein the high-temperature nickel-based alloy HRED6 comprises the following components in parts by weight: 48.0-50.0% of nickel, 27.0-30.0% of chromium, 4.0-6.0% of tungsten, 1.2-2.0% of silicon, 1.2-1.8% of niobium, 0.40-0.45% of carbon, 0.5-1.5% of manganese, less than 0.5% of cobalt, less than or equal to 0.05% of nitrogen, less than 0.035% of phosphorus and less than 0.03% of sulfur. The invention reasonably optimizes the element composition in the nickel-based alloy and optimizes the preparation method to prepare the high-temperature nickel-based alloy HRED6, compared with the prior nickel-based alloy, the high-temperature nickel-based alloy has obviously improved high-temperature characteristic, still has excellent tensile strength, fracture toughness, endurance life, corrosion resistance and other properties under the high-temperature treatment condition of 1200 ℃,wherein the tensile strength is more than or equal to 744MPa, the yield strength is more than or equal to 832MPa, and the fracture toughness is more than or equal to 42.8 MPa.m 1/2 The elongation at break is more than or equal to 9.3 percent, the endurance life is more than or equal to 367h, and the relative corrosion rate is less than or equal to 41.3 percent, so that the phenomena of deformation, cracking and the like are not easy to occur in the heat treatment process of the tool, the service life of the tool is prolonged, and the production efficiency is further improved.)

1. A high-temperature nickel-based alloy HRED6 is characterized in that the high-temperature nickel-based alloy HRED6 comprises the following components in parts by weight:

the balance being iron.

2. The high temperature nickel-based alloy HRED6 of claim 1, wherein the high temperature nickel-based alloy HRED6 comprises the following components in parts by weight:

the balance being iron.

3. The high-temperature nickel-based alloy HRED6 of claim 1, wherein the high-temperature nickel-based alloy HRED6 has tensile strength not less than 744MPa, yield strength not less than 832MPa and fracture toughness not less than 42.8 MPa-m at 1200 ℃^1/2The elongation at break is more than or equal to 9.3 percent, the durable service life is more than or equal to 367 hours, and the relative corrosion rate is less than or equal to 41.3 percent.

4. A method of making a high temperature nickel-base alloy HRED6 as set forth in any one of claims 1-3, comprising:

step 1, putting raw materials into an intermediate frequency furnace for heating and melting;

step 2, all the components are completely melted to obtain molten steel, and when the temperature reaches 1500-1600 ℃, manganese and silicon are sequentially added for pre-deoxidation;

step 3, after the sampling analysis component is qualified, continuously heating to the highest melting temperature, stopping heating and standing;

and 4, when the temperature of the molten steel is reduced to the casting temperature, adding silicon, calcium and barium to perform final deoxidation, and tapping after slag removal to obtain the high-temperature nickel-based alloy HRED 6.

5. The method of claim 4, wherein the starting materials in step 1 comprise: carburant, ferrocolumbium, ferrotungsten, metallic chromium or high carbon ferrochrome, electrolytic nickel and 304 stainless steel.

6. The method according to claim 4, wherein 0.5 mass% of manganese is added in step 2, and 0.25 mass% of silicon is added for pre-deoxidation.

7. The preparation method according to claim 4, wherein after the pre-deoxidation in the step 2, a deslagging agent is added for deslagging for 1-2 times.

8. The method of claim 4, wherein the maximum melting temperature in step 3 is 1700 ℃.

9. The preparation method according to claim 4, wherein the amount of the silicon, calcium and barium added in the step 4 is 0.1% of the mass of the molten steel.

10. The method according to claim 4, wherein an inserted thermocouple is used to measure the temperature of the molten steel in step 4.

Technical Field

The invention belongs to the technical field of high-temperature alloys, and particularly relates to a high-temperature nickel-based alloy HRED6 and a preparation method thereof.

Background

The nickel-based alloy is an alloy with comprehensive properties such as high strength, certain oxidation and corrosion resistance and the like at a high temperature of 650-1000 ℃. The alloy is further divided into nickel-based heat-resisting alloy, nickel-based corrosion-resisting alloy, nickel-based wear-resisting alloy, nickel-based precision alloy, nickel-based shape memory alloy and the like according to the main properties. The alloy is widely applied to the mechanical industry fields of automobiles, ships, aviation and the like, and is made into parts such as gears, bearings and the like. The parts such as gears, bearings and the like can be obtained after special heat treatment at high temperature close to 1200 ℃, the parts meeting the use mechanical properties can be obtained, the conditions of high temperature, high bearing, repeated cold and hot alternate use and the like in the heat treatment process are relatively severe, the proportion of common heat-resistant steel materials and the control of a smelting process can not meet the use working condition requirements, and the heat treatment tool generally has the phenomena of deformation, cracking and the like in 60-80 circulation processes, so that the service life of the heat treatment tool is influenced. Therefore, higher requirements are continuously put on the heat bearing capacity of the parts. The addition of Re element can raise the high temperature resistance of the alloy, but Re is one of the rarest elements in earth's crust, and is expensive and unsuitable for wide use. Therefore, a nickel-based alloy with low cost and high temperature resistance is needed.

Disclosure of Invention

The invention aims to provide a high-temperature nickel-based alloy HRED6 and a preparation method thereof, wherein the composition of the nickel-based alloy is optimized, the smelting process is further optimized, and the oxygen content of the high-temperature nickel-based alloy HRED6 is remarkably reduced through two steps of pre-deoxidation and final deoxidation, so that the tensile strength, fracture toughness, lasting life and other properties of the alloy under high-temperature treatment are remarkably improved, the problem that the alloy is easy to deform and crack during high-temperature heat treatment in the tool preparation process is avoided, and the production efficiency is improved.

In order to achieve the purpose, the invention adopts the technical scheme that:

a high-temperature nickel-based alloy HRED6 comprises the following components in parts by weight:

wherein, nickel Ni is the basis of nickel-based alloy, can be infinitely mutually dissolved with iron, expands the austenite region of the iron, is a main alloy element for forming and stabilizing austenite, and can also increase the strength, plasticity, toughness and fatigue property. However, in order to further improve various properties of the nickel-base alloy, other alloy elements also need to be added into the nickel-base alloy. In the invention, the content of nickel is controlled to be 48.0-50.0%.

The chromium Cr is the key for improving the high-temperature resistance and corrosion resistance of the alloy, can form a stable compound with carbon, improves the stability of a matrix, improves the antioxidation of the alloy and increases the corrosion resistance of steel; however, excessive addition of chromium may reduce the toughness of the alloy. In the invention, the content of chromium is controlled to be 27.0-30.0%.

Tungsten W is a solid solution strengthening element capable of forming a solid solution with nickel, which can form carbides with carbon having high strength and wear resistance, thereby increasing the strength of the alloy, whereas excessive addition of tungsten affects the structural stability of the alloy at high temperature, reducing its high temperature performance. In the invention, the content of tungsten is controlled to be 4.0-6.0%

Silicon Si is also one of the strengthening elements, which not only can improve the strength, hardness, hardenability and other properties of the alloy, but also can be used as a deoxidizer for deoxidation in the alloy smelting process, however, the toughness and fatigue property of the alloy can be reduced when the content is too high. In the invention, the content of silicon is controlled to be 1.2-2.0%.

Niobium Nb is also one of the strengthening elements, has excellent high temperature resistance and corrosion resistance, improves the hardness and fatigue performance of the alloy, and can obviously reduce the plasticity and toughness of the nickel-based alloy when being added in too much amount. In the invention, the content of niobium is controlled to be 1.2-1.8%.

The addition of carbon C can improve the hardness and the abrasion resistance of the nickel-based alloy, but the excessive addition can affect the creep property and the low-cycle fatigue property of the nickel-based alloy. In the invention, the content of carbon is controlled to be 0.40-0.45%.

Manganese Mn is one of solid solution strengthening elements capable of forming a solid solution with nickel, can improve the hardness and brittleness of the nickel-based alloy, can be used as a deoxidizer to play a role in an alloy smelting process, and can affect the high-temperature resistance of the nickel-based alloy when being added excessively. In the invention, the content of manganese is controlled to be 0.5-1.5%.

Cobalt Co has influence on the high temperature resistance of the nickel-based alloy, and nitrogen N, phosphorus P and sulfur S are adverse elements of the nickel-based alloy and can seriously affect the plasticity, brittleness and fatigue performance of the nickel-based alloy, so that in the invention, the content of cobalt is controlled to be less than 0.5 percent, the content of nitrogen is controlled to be less than or equal to 0.05 percent, the content of phosphorus is controlled to be less than 0.035 percent and the content of sulfur is controlled to be less than 0.03 percent.

Further, the high-temperature nickel-based alloy HRED6 comprises the following components in parts by weight:

further, the high-temperature nickel-based alloy HRED6 has tensile strength not less than 744MPa, yield strength not less than 832MPa and fracture toughness not less than 42.8 MPa.m at 1200 DEG C^1/2The elongation at break is more than or equal to 9.3 percent, the durable service life is more than or equal to 367 hours, and the relative corrosion rate is less than or equal to 41.3 percent.

The invention also provides a preparation method of the high-temperature nickel-based alloy HRED6, which comprises the following steps:

step 1, putting raw materials into an intermediate frequency furnace for heating and melting;

step 2, all the components are completely melted to obtain molten steel, and when the temperature reaches 1500-1600 ℃, manganese and silicon are sequentially added for pre-deoxidation;

step 3, after the sampling analysis component is qualified, continuously heating to the highest melting temperature, stopping heating and standing;

and 4, when the temperature of the molten steel is reduced to the casting temperature, adding silicon, calcium and barium to perform final deoxidation, and tapping after slag removal to obtain the high-temperature nickel-based alloy HRED 6.

Further, the raw materials in step 1 comprise: carburant, ferrocolumbium, ferrotungsten, metallic chromium or high carbon ferrochrome, electrolytic nickel and 304 stainless steel.

Further, in the step 2, 0.5 mass percent of manganese is added, and 0.25 mass percent of silicon is added for pre-deoxidation.

And further, after the pre-deoxidation in the step 2 is finished, adding a deslagging agent to carry out deslagging for 1-2 times.

Further, the maximum melting temperature in step 3 is 1700 ℃.

Further, the adding amount of the silicon, calcium and barium in the step 4 is 0.1 percent of the mass of the molten steel.

Further, in the step 4, an inserted thermocouple is adopted to measure the temperature of the molten steel.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, through reasonably optimizing various element components and contents in the nickel-based alloy and further optimizing the preparation method, the oxygen content in the high-temperature nickel-based alloy HRED6 is remarkably reduced through two steps of pre-deoxidation and final deoxidation, and the high-temperature nickel-based alloy HRED6 is prepared^1/2The elongation at break is more than or equal to 9.3 percent, the endurance life is more than or equal to 367h, and the relative corrosion rate is less than or equal to 41.3 percent, so that the phenomena of deformation, cracking and the like are not easy to occur in the heat treatment process of the tool, the service life of the tool is prolonged, and the production efficiency is further improved.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The embodiment provides a high-temperature nickel-based alloy HRED6 and a preparation method thereof, and the preparation method specifically comprises the following steps:

(1) the formula comprises the following components in parts by weight: 48.0-50.0% of nickel, 27.0-30.0% of chromium, 4.0-6.0% of tungsten, 1.2-2.0% of silicon, 1.2-1.8% of niobium, 0.40-0.45% of carbon, 0.5-1.5% of manganese, less than 0.5% of cobalt, less than or equal to 0.05% of nitrogen, less than 0.035% of phosphorus, less than 0.03% of sulfur and the balance of iron, and the raw materials of a carburant, ferrocolumbium, ferrotungsten, high-carbon ferrochromium, electrolytic nickel and 304 stainless steel are respectively loaded into an intermediate frequency furnace according to the size and sequence of the materials, and power transmission is started after the materials are loaded, so that the melting speed is accelerated, the contact time of the steel material in the atmosphere is shortened, and the oxidation and the gas absorption are reduced.

(2) And completely melting the steel materials to obtain molten steel, adding 0.5 mass percent of manganese and 0.25 mass percent of silicon for pre-deoxidation when the temperature reaches 1500-1600 ℃ and about 1550 ℃, and covering the molten steel with a Ishikawa No. 2 slag remover for slagging for 1-2 times.

(3) Sampling and carrying out spectral analysis, analyzing the composition of each element, and analyzing that the high-temperature nickel-based alloy comprises the following components in parts by weight: 48.8 percent of nickel, 29.5 percent of chromium, 5.2 percent of tungsten, 2.0 percent of silicon, 1.4 percent of niobium, 0.40 percent of carbon, 1.2 percent of manganese, less than 0.5 percent of cobalt, less than or equal to 0.05 percent of nitrogen, less than 0.035 percent of phosphorus, less than 0.03 percent of sulfur and the balance of iron. The components are qualified, the molten steel is melted and continuously heated to the maximum melting temperature of 1700 ℃, the power supply is immediately turned off, the molten steel is kept stand for 2 to 3 minutes, and simultaneously, the surface of the molten steel is covered with a slag removing agent.

(4) After the molten steel is stood still, the temperature is measured by using an insertion type thermocouple, when the temperature is close to the pouring temperature, silicon, calcium and barium with the mass fraction of 0.1 percent are added into the molten steel for final deoxidation, after the final deoxidation is finished, a steel bar is used for removing large covering slag, then a Ishikawa No. 2 slag remover is scattered on the surface of the molten steel, the covering slag is dipped and removed by using the steel bar, the slag is repeatedly beaten for 1 to 2 times, and then the steel can be discharged from a steel ladle, so that the high-temperature nickel-based alloy HRED6 is prepared.

Example 2

The difference between the embodiment and the embodiment 1 is that after the spectral analysis in the step (3), the composition of each element comprises the following components in parts by weight: 50.0 percent of nickel, 27.2 percent of chromium, 4.1 percent of tungsten, 1.7 percent of silicon, 1.2 percent of niobium, 0.41 percent of carbon, 0.6 percent of manganese, less than 0.5 percent of cobalt, less than or equal to 0.05 percent of nitrogen, less than 0.035 percent of phosphorus, less than 0.03 percent of sulfur and the balance of iron.

Example 3

The difference between the embodiment and the embodiment 1 is that after the spectral analysis in the step (3), the composition of each element comprises the following components in parts by weight: 48.1 percent of nickel, 28.8 percent of chromium, 6.0 percent of tungsten, 1.2 percent of silicon, 1.8 percent of niobium, 0.45 percent of carbon, 1.5 percent of manganese, less than 0.5 percent of cobalt, less than or equal to 0.05 percent of nitrogen, less than 0.035 percent of phosphorus, less than 0.03 percent of sulfur and the balance of iron.

Example 4

The difference between the embodiment and the embodiment 1 is that after the spectral analysis in the step (3), the composition of each element comprises the following components in parts by weight: 48.7 percent of nickel, 28.8 percent of chromium, 4.9 percent of tungsten, 2.0 percent of silicon, 1.7 percent of niobium, 0.43 percent of carbon, 1.3 percent of manganese, less than 0.5 percent of cobalt, less than or equal to 0.05 percent of nitrogen, less than 0.035 percent of phosphorus, less than 0.03 percent of sulfur and the balance of iron.

Comparative example 1

This comparative example differs from example 1 in that: the nickel-based alloy comprises the following elements in parts by weight: 48.7 percent of nickel, 28.8 percent of chromium, 7.3 percent of tungsten, 2.0 percent of silicon, 0.9 percent of niobium, 0.43 percent of carbon, 0.3 percent of manganese, 0.7 percent of cobalt, less than or equal to 0.05 percent of nitrogen, less than 0.035 percent of phosphorus, less than 0.03 percent of sulfur and the balance of iron.

Comparative example 2

This comparative example differs from example 1 in that: in the step (2), the step of adding manganese and silicon for pre-deoxidation is omitted.

Comparative example 3

This comparative example differs from example 1 in that: in the step (2), silicon, calcium and barium with the mass fraction of 0.1% are adopted for pre-deoxidation, and in the step (4), manganese with the mass fraction of 0.5% and silicon with the mass fraction of 0.25% are sequentially added for final deoxidation.

Evaluation protocol

The properties of the nickel-based alloys prepared in examples 1 to 4 and comparative examples 1 to 3, such as tensile strength, yield strength, fracture toughness, elongation at break, endurance life, and relative corrosion rate (GB/T10125-.

TABLE 1 mechanical Properties of different nickel-based alloys

According to the performance measurement results in Table 1, the high-temperature nickel-based alloy HRED6 still has excellent performance under the high-temperature treatment condition of 1200 ℃, wherein the tensile strength is more than or equal to 744MPa, the yield strength is more than or equal to 832MPa, and the fracture toughness is more than or equal to 42.8 MPa.m^1/2The elongation at break is more than or equal to 9.3 percent, the durable service life is more than or equal to 367 hours, and the relative corrosion rate is less than or equal to 41.3 percent. Compared with the high-temperature nickel-based alloy HRED6, when the contents of tungsten and cobalt in the element composition are increased and the contents of niobium and manganese are reduced (comparative example 1), the mechanical property and the corrosion resistance of the nickel-based alloy under the high-temperature condition are obviously reduced, namely the high-temperature resistance is obviously reduced; when the pre-deoxidation step is omitted or the order of the deoxidizers used in the two deoxidation steps is changed in the preparation method of the nickel-based alloy, the high-temperature resistance of the prepared high-temperature nickel-based alloy is also significantly influenced.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.