CN108715951B - Multiphase-structure nickel-chromium-iron-series high-temperature alloy and preparation method thereof - Google Patents
Multiphase-structure nickel-chromium-iron-series high-temperature alloy and preparation method thereof Download PDFInfo
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- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
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Abstract
The invention relates to a nickel-chromium-iron series high-temperature alloy with a multiphase structure and a preparation method thereof, wherein the alloy comprises the following components in percentage by weight: ni: 35.0-45.0%; cr: 30.0-42.0%; fe: the balance; w: 0 to 3.00 percent; nb: 0 to 3.00 percent; c: 0.30-1.10%; si is less than or equal to 2.00 percent; mn is less than or equal to 2.00 percent; al is less than or equal to 1.00 percent; b is less than or equal to 0.02 percent; v is less than or equal to 1.00 percent; s is less than or equal to 0.035%; p is less than or equal to 0.035%; la is less than or equal to 0.5 percent. The W, Nb, C, Si, Mn, Al, B, V, La and the like in the components of the alloy play roles in solid solution, grain boundary and two-phase strengthening, the high-purity smelting and electroslag remelting duplex metallurgy process technology is adopted, the structural mechanical property of the alloy is improved through hot working and heat treatment, and the obtained alloy has the properties of carburization resistance, coking resistance, vulcanization resistance, oxidation resistance, corrosion resistance and wear resistance.
Description
Technical Field
The invention relates to a nickel-chromium-iron high-temperature alloy, in particular to a nickel-chromium-iron high-temperature alloy with a multiphase structure and a preparation method thereof.
Background
Under the environmental conditions of carbon plants, coking furnaces, molten silicates and molten sulfates, alloy materials with high temperature and high strength, excellent oxidation resistance and good corrosion resistance are needed, and parts which can work for a long time under the high-stress and high-temperature corrosion conditions, such as protection pipes, leakage plates, vent pipes, superheater pipes, overflow ports, spray pipes, towers and other device parts, are manufactured.
Parts operating under different environmental conditions have different requirements on materials, and both the properties and the processability of the materials are required, and the material economy is further considered.
At present, alloy materials usable under environmental conditions such as carbon plants, coke ovens, molten silicates, molten sulfates and the like include alloy materials such as K407, GH5K, GH3007, MGH4755 and the like, which have limitations and are not economical. Such as: the K407 casting alloy has low plasticity and is not easy to be made into complex parts; MGH4755 dispersion strengthened alloy has poor machinability and is difficult to be made into large and large pieces; GH3007 has low strength and insufficient high-temperature resistance; even if the comprehensive properties of GH5k such as high-temperature and high-strength, oxidation resistance and corrosion resistance are relatively good, the requirements of the processing characteristics and service working condition of parts are difficult to meet, so that the workability, service life and reliability of the parts are influenced.
Disclosure of Invention
The invention aims to provide a nickel-chromium-iron high-temperature alloy with a multiphase structure and a preparation method thereof. The alloy is a multiphase composite reinforced alloy, has the characteristics of coking resistance, carburization resistance, vulcanization resistance, oxidation resistance and abrasion resistance, excellent corrosion resistance, excellent high-temperature high-strength capability and better hot working plasticity, and is suitable for manufacturing parts which bear lasting stress at high temperature and work in various strong-corrosion service environments.
The nickel-chromium-iron high-temperature alloy comprises the following components in percentage by weight: ni: 35.0-45.0%; cr: 30.0-42.0%; fe: the balance; w: 0 to 3.00 percent; nb: 0 to 3.00 percent; c: 0.30-1.10%; si is less than or equal to 2.00 percent; mn is less than or equal to 2.00 percent; al is less than or equal to 1.00 percent; b is less than or equal to 0.02 percent; v is less than or equal to 1.00 percent; s is less than or equal to 0.035%; p is less than or equal to 0.035%; la is less than or equal to 0.5 percent.
The nickel-chromium-iron high-temperature alloy has the better technical scheme that C: 0.30-0.80%; cr: 32.0 to 37.0 percent; ni: 37.0 to 43.0 percent; nb: 0.75-2.00%; w: 0.25-2.00%; si: 1.00-2.00%; mn is less than or equal to 1.00 percent; al: 0.15-0.30%; b: 0.004-0.01%; v: 0.05-0.2%; s is less than or equal to 0.01 percent; p is less than or equal to 0.015 percent; la: 0.1-0.2%; the balance being Fe.
The W + Nb content in the components is 1-3% so as to ensure the high-temperature high-strength and wear-resistant performance of the alloy; al + B + V + La is less than or equal to 0.8 percent, which not only ensures the mechanical property of the alloy, but also maintains good hot-working performance.
The alloy has multiphase structure of GAMMA + M23C6+ G + MC or GAMMA + M23C6+ G + SIGMA or GAMMA + M23C6+G +BCC。
The preparation method of the nickel-chromium-iron high-temperature alloy comprises the following steps:
1) vacuum induction furnace melting
According to the proportion, Ni, Cr, Fe, Nb and W are put into a crucible of a vacuum induction furnace, and are refined for 15-45 minutes at 1550-1650 ℃ after being melted, and the vacuum degree is more than or equal to 5 Pa; c, Si and Mn are added, refining is carried out for 10-25 minutes at 1500-1600 ℃ after melting, and the vacuum degree is superior to 3 Pa; filling argon to protect, adding Al, V, B and La, melting, refining at 1450-1550 ℃ for 5-15 minutes, and casting to form an electroslag remelting electrode rod;
2) electroslag remelting
With CaF2、Al2O3CaO, MgO and SiO2Heating the slag to a molten state as slag, pouring the slag into an electroslag furnace crystallizer, descending an electroslag remelting electrode rod obtained in the step 1), inserting the electroslag remelting electrode rod into the molten slag, electrifying, adjusting remelting current, wherein the current is 4000 +/-1500A and the voltage is 43 +/-5V, slowly melting the electrode rod, and enabling molten steel drops to penetrate through a molten slag layer to be solidified into an electroslag ingot;
3) hot working
Heating the electroslag ingot obtained in the step 2) to 1080-1220 ℃, preserving heat for 1-4 h, and carrying out hot processing at 1040-1180 ℃ to obtain a bar;
4) thermal treatment
Carrying out solution heat treatment on the bar in the step 3), wherein the technological parameters are as follows: water quenching at 1040-1120 ℃ for 0.5-2.5 h.
The slag charge in the step 2) comprises the following components in percentage by weight: CaF 250 to 70% of Al2O310 to 30%, CaO 5 to 15%, MgO 0 to 10%, SiO 20 to 8%.
When W + Nb is 1-3%; when Al + B + V + La is less than or equal to 0.8%, the mechanical property of the alloy obtained in the step 4) after solution treatment is as follows: tensile strength Rm is more than or equal to 800MPa, yield strength Rp0.2 is more than or equal to 450MPa, elongation A is more than or equal to 30%, and the tensile strength Rm is more than or equal to 1100 ℃: the tensile strength Rm is more than or equal to 65MPa, the yield strength Rp0.2 is more than or equal to 40MPa, and the elongation A is more than or equal to 30 percent.
The high-temperature alloy provided by the invention has the following main elements:
ni is expensive, but can dissolve more Cr, Fe, Nb, W, Si and other alloy elements as an alloy matrix for alloying, and still maintain the stability of a gamma austenite phase, thereby ensuring the strength, toughness and corrosion resistance of the alloy.
Cr can raise the heat stability of the alloy, and Cr-rich alloy can be formed by adding Cr2O3By solid solution strengthening of Cr, MC, Cr23C6The second phase strengthening is performed to improve the heat resistance and the wear resistance of the alloy, and the higher the second phase strengthening is, the greater the deformation difficulty is.
Fe reduces the corrosion resistance of the alloy, but is cheap, when the Fe is added into the expensive high-temperature alloy taking nickel as a matrix, the cost can be reduced, the lattice constant of the Fe is different from that of the nickel by 3 percent, and a long-range stress field is caused due to lattice expansion to block dislocation motion. The stacking fault energy of the nickel-based austenite is reduced, the solid solution strengthening effect is achieved, the alloy yield strength is improved, and the alloy has good comprehensive performance.
C is an austenite strong forming element, so that expensive austenite matrix nickel elements are saved. Part of C is dissolved in the gamma solid solution to cause lattice distortion and generate elastic stress field strengthening, thereby improving the strength of the gamma solid solution and playing a role in solid solution strengthening; part of the carbide M forms a series of carbides with Cr, Nb and W23C6、M7C3、M6C and M2(C, N), mainly distributed in the grain boundary, the grain boundary strengthening; the more the content of C is, the higher the heat resistance of the alloy is, but the higher the heat resistance is, the processing difficulty is increased, so that the percentage content of C in the invention is 0.3-1.10%.
Si is dissolved in nickel-based austenite to improve the strength of the alloy and the capability of resisting corrosion of molten sulfate, and a layer of SiO can be formed in an oxidizing atmosphere by adding Si2Film, and high-temperature oxidation resistance of the alloy is improved.
Nb is dissolved in Ni-based austenite alloy to play a role in solid solution strengthening and carbon fixation, the high-temperature performance of the alloy is improved, part of Nb and C form MC type carbide, and the MC type carbide and the C are decomposed to form a low-carbon high-Nb compound M in the heat treatment or use process23C6Or M6C is mainly distributed in crystal boundary and crystal-forming boundary for strengthening, can improve the corrosion and abrasion resistance of the alloy, and excessively increases the deformation resistance.
In addition to carbide formation, W is partially dissolved in solid solution in the alloy and has the main effect of increasing the red hardness, the hot strength and the increased wear resistance due to carbide formation of the alloy, too high also increasing the difficulty of the working process.
The alloy comprises a certain amount of W and Nb so as to improve the corrosion resistance, wear resistance and impact resistance of the alloy, wherein the content of W and Nb is 1-3%.
The Al, B, V and La elements play roles in purifying tissues and refining grains, the processing performance, the heat resistance, the wear resistance, the oxidation resistance and the corrosion resistance of the alloy are comprehensively improved, and the total percentage content of the Al, B, V and La elements is controlled to be not more than eight zeros.
The alloy has the beneficial effects that: Ni-Cr-Fe system is used as alloy matrix, C, Nb, W and Si are alloyed together, and Al, B, V and La elements are microalloyed together, so that the alloy has the properties of carburization resistance, coking resistance, vulcanization resistance, oxidation resistance, corrosion resistance, wear resistance and high-temperature endurance stress resistance. By adopting the duplex metallurgical process of vacuum melting and electroslag remelting, the alloy composition is purified, the alloy structure performance is improved, and the processability of alloy materials, the use characteristics of structural components and the economical efficiency are guaranteed. Compared with several alloys in the background art, the high-temperature alloy has obvious advantages in the aspects of heat resistance, corrosion resistance, abrasion resistance, economy and the like.
The high-temperature alloy can be used for structural parts such as protection tubes, leakage plates, vent pipes, superheater tubes, overflow ports, spray pipes, towers and the like under complex and severe environmental conditions such as anti-carburization and refractory (silicic acid, sulfuric acid and nitric acid) salts.
The invention will now be further described with reference to specific embodiments, but the invention is not limited thereto.
Drawings
FIG. 1 is a microstructure of an alloy of the present invention after solution heat treatment;
FIG. 2 is a phase composition graph of the alloy of the present invention.
Detailed Description
The alloy of the invention comprises the following components and contents as shown in Table 1:
TABLE 1 content of Ni-Cr-Fe-based superalloy component
The high-temperature alloy is prepared by the following method:
1) vacuum induction furnace melting
Putting Ni, Nb, W, Cr and Fe into a vacuum induction furnace according to the proportion, refining for 15-45 minutes at 1550-1650 ℃ after melting, wherein the vacuum degree is superior to 5 Pa; c, Si and Mn are added, refining is carried out for 10-25 minutes at 1500-1600 ℃ after melting, and the vacuum degree is superior to 3 Pa; filling argon to protect, adding Al, B, V and La, melting, refining at 1450-1550 ℃ for 5-15 minutes, and casting to form an electroslag remelting electrode rod;
2) electroslag remelting
With CaF2、Al2O3CaO, MgO and SiO2As a slag charge, the slag charge comprises the following components in percentage by weight: CaF 250 to 70% of Al2O310 to 30%, CaO 5 to 15%, MgO 0 to 10%, SiO2Heating the slag to a molten state in an amount of 0 to 8%. Inserting the electrode rod obtained in the step 1) into a crystallizer, descending to a position close to an electroslag furnace bottom plate, pouring molten slag, electrifying, adjusting the electroslag remelting current, wherein the current is 4000 +/-1500A and the voltage is 43 +/-5V, slowly melting the electrode rod, enabling molten steel drops to penetrate through the molten slag layer, and remelting electroslag into an electroslag ingot;
3) hot working
Heating the electroslag ingot obtained in the step 2) to 1080-1220 ℃, preserving heat for 1-4 h, and carrying out hot processing at 1040-1180 ℃ to obtain a bar;
4) thermal treatment
Carrying out solution heat treatment on the bar in the step 3), wherein the technological parameters are as follows: water quenching at 1040-1120 ℃ for 0.5-2.5 h;
table 2 shows the technical parameters and performance test results for the superalloy preparation described in table 1:
TABLE 2 technical parameter of Ni-Cr-Fe series high-temperature alloy preparation and performance test results
Claims (5)
1. The nickel-chromium-iron high-temperature alloy with the multiphase structure is characterized by comprising the following components in percentage by weight: 0.30-1.10%; cr: 30.0-42.0%; ni: 35.0-45.0%; nb: 0 to 3.00 percent; w: 0 to 3.00 percent; si is less than or equal to 2.00 percent; mn is less than or equal to 2.00 percent; al is less than or equal to 1.00 percent; b is less than or equal to 0.02 percent; v is less than or equal to 1.00 percent; s is less than or equal to 0.035%; p is less than or equal to 0.035%; la is less than or equal to 0.5 percent; the balance being Fe; al + B + V + La in the alloy component is less than or equal to 0.8%, and W + Nb in the alloy component is 1-3%;
the alloy is prepared by the following steps:
1) vacuum induction furnace melting
According to the proportion, Ni, Cr, Fe, Nb and W are put into a crucible of a vacuum induction furnace, and are refined for 15-45 minutes at 1550-1650 ℃ after being melted, and the vacuum degree is more than or equal to 5 Pa; c, Si and Mn are added, refining is carried out for 10-25 minutes at 1500-1600 ℃ after melting, and the vacuum degree is superior to 3 Pa; filling argon to protect, adding Al, V, B and La, melting, refining at 1450-1550 ℃ for 5-15 minutes, and casting to form an electroslag remelting electrode rod;
2) electroslag remelting
With CaF2、Al2O3CaO, MgO and SiO2Heating the slag to a molten state as slag, pouring the slag into an electroslag furnace crystallizer, slowly descending the electroslag remelting electrode rod obtained in the step 1), inserting the electroslag remelting electrode rod into the molten slag, electrifying, adjusting remelting current, wherein the current is 4000 +/-1500A, the voltage is 43 +/-5V, slowly melting the electrode rod, and molten steel drops penetrate through a molten slag layer to be solidified into an electroslag ingot;
3) hot working
Heating the electroslag ingot obtained in the step 2) to 1080-1220 ℃, preserving heat for 1-4 h, and carrying out hot processing at 1040-1180 ℃ to obtain a bar;
4) thermal treatment
Carrying out solution heat treatment on the bar in the step 3), wherein the technological parameters are as follows: water quenching at 1040-1120 ℃ for 0.5-2.5 h.
2. The nickel-chromium-iron high-temperature alloy according to claim 1, which is characterized by comprising the following components in percentage by weight:
c: 0.30-0.80%; cr: 32.0 to 37.0 percent; ni: 37.0 to 43.0 percent; nb: 0.75-2.00%; w: 0.25-2.00%; si: 1.00-2.00%; mn is less than or equal to 2.00 percent; al: 0.15-0.30%; b: 0.004-0.01%; v: 0.05-0.2%; s is less than or equal to 0.01 percent; p is less than or equal to 0.015 percent; la: 0.1-0.2%; the balance being Fe.
3. The nichrome-iron-based superalloy according to any of claims 1-2, wherein: the alloy has multiphase structure of GAMMA + M23C6+ G + MC or GAMMA + M23C6+ G + SIGMA or GAMMA + M23C6+G +BCC。
4. The preparation method of the nickel-chromium-iron high-temperature alloy is characterized by comprising the following steps of:
1) vacuum induction furnace melting
According to the proportion of any one of claims 1-2, Ni, Cr, Fe, Nb and W are put into a crucible of a vacuum induction furnace, refined for 15-45 minutes at 1550-1650 ℃ after melting, and the vacuum degree is more than or equal to 5 Pa; c, Si and Mn are added, refining is carried out for 10-25 minutes at 1500-1600 ℃ after melting, and the vacuum degree is superior to 3 Pa; filling argon to protect, adding Al, V, B and La, melting, refining at 1450-1550 ℃ for 5-15 minutes, and casting to form an electroslag remelting electrode rod;
2) electroslag remelting
With CaF2、Al2O3CaO, MgO and SiO2Heating the slag to a molten state as slag, pouring the slag into an electroslag furnace crystallizer, slowly descending the electroslag remelting electrode rod obtained in the step 1), inserting the electroslag remelting electrode rod into the molten slag, electrifying, adjusting remelting current, wherein the current is 4000 +/-1500A, the voltage is 43 +/-5V, slowly melting the electrode rod, and molten steel drops penetrate through a molten slag layer to be solidified into an electroslag ingot;
3) hot working
Heating the electroslag ingot obtained in the step 2) to 1080-1220 ℃, preserving heat for 1-4 h, and carrying out hot processing at 1040-1180 ℃ to obtain a bar;
4) thermal treatment
Carrying out solution heat treatment on the bar in the step 3), wherein the technological parameters are as follows: water quenching at 1040-1120 ℃ for 0.5-2.5 h.
5. The method of claim 4, wherein: the slag charge in the step 2) comprises the following components in percentage by weight:
CaF250 to 70% of Al2O310 to 30%, CaO 5 to 15%, MgO 0 to 10%, SiO20 to 8%.
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