CN115717205A - High-temperature high-resistance nickel-based alloy and preparation method thereof - Google Patents
High-temperature high-resistance nickel-based alloy and preparation method thereof Download PDFInfo
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- CN115717205A CN115717205A CN202110972507.3A CN202110972507A CN115717205A CN 115717205 A CN115717205 A CN 115717205A CN 202110972507 A CN202110972507 A CN 202110972507A CN 115717205 A CN115717205 A CN 115717205A
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Abstract
The invention relates to a high-temperature high-resistance electrothermal alloy material, in particular to a high-temperature high-resistance nickel-based alloy and a preparation method thereof. The high-temperature high-resistance nickel-based alloy comprises the following elements: ni, C, si, mn, al, ti, cr, zr, Y, cu, nb, la, ce, B, fe, and the like. The preparation method comprises the following steps: proportioning, smelting, electroslag remelting, forging, hot rolling, acid washing, rinsing, trimming, polishing, multi-pass cold rolling or cold drawing, annealing and the like. The high-temperature high-resistance nickel-based alloy manufactured by the invention has the advantages of high-temperature oxidation resistance, high resistivity, high-temperature creep resistance and few high-temperature stripping oxides, overcomes the defects of the existing nickel-chromium alloy and iron-chromium-aluminum alloy technologies, and has good industrial application prospects.
Description
Technical Field
The invention relates to the technical field of nickel-based alloys, in particular to a high-temperature high-resistance nickel-based alloy and a preparation method thereof.
Background
The electrothermal alloy material provided by the prior art is a functional or structural material which converts electric energy into heat energy by utilizing the resistance characteristic of the material, and is widely applied to the fields of metallurgy, machinery, petrifaction, electricity, construction, military industry, household appliances, consumer electronics, new energy automobiles and the like and is used for manufacturing various electrothermal elements. The high-temperature electrothermal alloy is one of very important engineering core materials and plays an important role in national economy. The commonly used high temperature electrothermal alloys are mainly classified into two types: an iron-chromium-aluminum alloy having a ferritic structure and a nickel-chromium alloy having an austenitic structure. The iron-chromium-aluminum alloy system has the advantages of high use temperature, high resistivity, good high-temperature oxidation resistance and the like, but the iron-chromium-aluminum alloy is of a ferrite structure, ferrite grains grow rapidly at high temperature to greatly reduce creep strength, and the ferrite structure property of the iron-chromium-aluminum alloy causes poor corrosion resistance, and in addition, the iron-chromium-aluminum alloy system is easy to generate M23C6 during long-term use in a temperature range of 415-800 ℃, so that the alloy has very obvious brittleness. Therefore, the characteristics of reduced high-temperature creep strength, poor corrosion resistance, high-temperature brittleness and the like are key factors for limiting the use of the iron-chromium-aluminum alloy under high requirements. The nickel-chromium alloy system has excellent corrosion resistance, high-temperature creep strength, low resistivity and low working temperature, and is limited to the application fields with small volume and high resistivity.
Disclosure of Invention
The invention provides a high-temperature high-resistance nickel-based alloy and a preparation method thereof, and solves the problem that the existing alloy cannot integrate the advantages of high resistivity, high-temperature oxidation resistance, corrosion resistance and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
the high-temperature high-resistance nickel-based alloy comprises the following elements in percentage by mass:
C：0.1-0.3％；Cr：22-25％；Fe:7-10％；Si:<0.5％；Mn:<0.4％；Cu:0.05-0.15％；Al:2-4.5％；
Ti:0.15-0.45％；Zr:0.05-0.15％；La+Ce+Nb+Y:0.06-0.2％；P:<0.02％；S： <0.01％；B:0.01-0.02％；
and nickel and inevitable impurities.
A preparation method of a high-temperature high-resistance nickel-based alloy comprises the following steps:
s1, proportioning C, cr, fe, si, mn, cu, al, ti, zr, la, ce, nb, Y, P, S and B according to the element composition and the mass percent;
s2, placing the prepared raw materials into a vacuum induction smelting furnace, smelting, and cooling along with the furnace to form a first alloy ingot;
s3, carrying out electroslag remelting or vacuum consumable treatment on the first alloy ingot, purifying metal and carrying out cleaning treatment to obtain a second alloy ingot;
s4, discharging the second alloy ingot out of the furnace, immediately forging the second alloy ingot into a flat blank or a round bar, and performing air cooling treatment;
s5, heating the flat blank or the round bar, preserving heat, taking out of the furnace, carrying out hot rolling to obtain a strip or a wire rod, and carrying out air cooling to room temperature after the hot rolling;
s6, carrying out acid washing and rinsing on the strip or the wire rod to remove surface oxides;
and S7, performing cold rolling or cold drawing and annealing on the strip or wire rod with the surface oxide removed at least twice to obtain a strip and wire with the finished thickness.
Preferably, before the raw materials are smelted, the smelting furnace is vacuumized and filled with inert gas for protection.
Preferably, before hot rolling, the flat blank or the round bar is heated to 1200-1350 ℃ and is kept warm for 1-3 hours.
Preferably, the finishing temperature during hot rolling is 900-1200 ℃.
Preferably, the annealing temperature is 950-1150 ℃.
Through implementing above technical scheme, have following technological effect: the high-temperature high-resistance nickel-based alloy provided by the invention has the advantages of high resistivity of an iron-chromium-aluminum alloy, corrosion resistance, high-temperature strength of a nickel-chromium alloy and the like, and can be used at 1200 ℃ for a long time.
Detailed Description
In order to better understand the technical solution of the present invention, the following detailed description is provided of the examples provided by the present invention.
Example one
The high-temperature high-resistance nickel-based alloy provided by the embodiment comprises the following elements in percentage by mass:
C：0.1-0.3％；Cr：22-25％；Fe:7-10％；Si:<0.5％；Mn:<0.4％；Cu:0.05-0.15％； Al:2-4.5％；
Ti:0.15-0.45％；Zr:0.05-0.15％；La+Ce+Nb+Y:0.06-0.2％；P:<0.02％；S： <0.01％；B:0.01-0.02％；
and nickel and unavoidable impurities.
The high-temperature high-resistance nickel-based alloy comprises the following elements:
the higher C element is a main strengthening element in the high-temperature high-resistance alloy, the C exists as a gap element, the resistance can be obviously improved, and the C is combined with the Ti which is the most C element to form a TiC nano precipitate, so that the formation of M23C6 is inhibited, the grain boundary is nailed, the crystal grain is refined, and the resistivity is improved. The composition of the carbon is accurately controlled so that the carbon has extremely high temperature creep-cracking resistance.
The Cr element is another important element in the nickel-chromium alloy, and mainly has the effects of improving oxidation resistance, increasing corrosion resistance, improving alloy strength and improving resistivity.
The main function of the Si element is to stabilize the components of the alloy and to homogenize the alloy structure. The problem of material hardening caused by Al in the alloy to impair the workability of the alloy can be partially solved by adding Si instead of Al. Si reduces the resistance temperature coefficient and the thermal potential of the alloy to copper on one hand, and increases the inherent resistance of the alloy on the other hand; however, excessive Si significantly impairs the workability of the alloy, and therefore the amount of Si added is within 0.5%.
The addition of Mn element can improve the processing property of the alloy and the stability of the electrical property of the alloy, and can improve the tensile strength and the high-temperature creep property of the alloy. However, since too high a manganese content impairs the high-temperature oxidation resistance, the Mn content should be controlled to be within 0.4%.
Al element is the most important element in the oxidation resistance of the high-temperature high-resistance nickel-based alloy, and the resistivity and the service temperature of the alloy are obviously improved. The formed Al2O3 oxide film can effectively protect the further oxidation of the internal structure. So that it can be used at high temperature of 1200 c.
The addition of Ti element can form TiC educt with C, and inhibit the formation of harmful substances such as M23C6, on one hand, the pinning grain boundary can effectively prevent the grain growth at high temperature, refine the grain, improve the high-temperature creep strength, and simultaneously improve the resistivity. On the other hand, tiO formed at high temperature strengthens an Al2O3 oxide film formed on the alloy surface, improves the compactness of the oxide film and greatly reduces the peelability.
The N element and Ti can form large-size TiN inclusions, which are unfavorable for the alloy, and the N content needs to be strictly controlled to be less than 20PPM.
The addition of the B element can well fix the harmful N element, and can also effectively pin grain boundaries and refine grains.
The La, ce, nb and Y rare earth elements can pin the grain boundary, inhibit the growth of grains so as to refine the grains, form an oxide film and obviously improve the high-temperature oxidation resistance of the alloy.
The high-temperature oxidation resistance of the alloy is improved by adding Zr element. The addition of trace zirconium element can still better control the coarsening of crystal grains when the high-temperature working at more than 1000 ℃ is carried out.
Example two
The preparation method of the high-temperature high-resistance nickel-based alloy provided by the embodiment comprises the following steps of:
s1, proportioning C, cr, fe, si, mn, cu, al, ti, zr, la, ce, nb, Y, P, S and B according to the element composition and the mass percent;
s2, placing the prepared raw materials into a vacuum induction smelting furnace, smelting, and cooling along with the furnace to form a first alloy ingot;
s3, carrying out electroslag remelting or vacuum consumable treatment on the first alloy ingot, purifying metal and carrying out cleaning treatment to obtain a second alloy ingot;
s4, discharging the second alloy ingot out of the furnace, immediately forging the second alloy ingot into a flat blank or a round bar, and performing air cooling treatment;
s5, heating the flat blank or the round bar, preserving heat, taking the blank or the round bar out of the furnace, carrying out hot rolling on the blank or the round bar to obtain a strip or a wire rod, and carrying out air cooling on the hot rolled strip or the wire rod to room temperature;
s6, carrying out acid washing and rinsing on the strip or the wire rod to remove surface oxides;
and S7, performing cold rolling or cold drawing and annealing on the strip or wire rod with the surface oxide removed at least twice to obtain a strip and wire with the finished thickness.
Before the raw materials are smelted, the smelting furnace is vacuumized and is filled with inert gas for protection. Before hot rolling, heating the flat blank or the round bar to 1200-1350 ℃, and preserving heat for 1-3 hours. The finishing temperature in hot rolling is 900-1200 ℃.
The specific operation of at least twice cold rolling or cold drawing is as follows: a first cold rolling to a 3mm thick strip or cold drawing to a 3mm diameter wire, a second cold rolling to a 1.5mm thick strip or cold drawing to a 1.5mm diameter wire, a third cold rolling to a 0.7mm thick strip or cold drawing to a 0.7mm diameter wire, a fourth cold rolling to a 0.3mm thick strip or cold drawing to a 0.3mm diameter wire, and a fifth cold rolling to a 0.1-0.15mm thick strip or cold drawing to a 0.1-0.15mm diameter wire. And the sixth cold rolling to a strip with the thickness of 0.05-0.1mm or cold drawing to a wire with the diameter of 0.05-0.1 mm. The intermediate annealing temperature is 950-1150 ℃. After cold rolling or cold drawing, cleaning and drying to obtain the finished product.
The invention is further illustrated and understood by the following examples three-five.
The element ratios of examples three to five are shown in table 1.
Table 1 elemental composition (wt%) of examples three-five are as follows (alloys with designations 1, 2, 3 are example one, example two, and example three, respectively)
TABLE 1
(1) Preparing materials: preparing materials according to the element proportion in the table 1;
(2) Smelting: putting the raw materials into a vacuum induction melting furnace, vacuumizing, filling inert gas for protection, and cooling the raw materials into an alloy ingot along with the furnace after melting;
(3) Electroslag remelting: performing heat treatment in a vacuum furnace, purifying metal and obtaining an alloy ingot with a clean, uniform and compact structure;
(4) Forging: discharging the alloy ingot subjected to electroslag remelting, immediately forging the alloy ingot into a flat blank, cooling the blank in air, and removing the head and the tail of the blank;
(5) Hot rolling: heating the forged flat blank to 1200-1350 ℃, preserving heat for 1-3 hours, discharging the blank from a furnace, carrying out hot rolling to obtain a strip with the thickness of 5.5mm, carrying out finish rolling at the temperature of 900-1200 ℃, and cooling the strip in air to room temperature after rolling;
(6) Acid washing: sand blasting, acid washing, rinsing and drying the hot rolled strip to remove surface oxides;
(7) Cold rolling and annealing: cold rolling or cold drawing and annealing for multiple times, wherein the cold rolling is carried out for the first time to obtain a strip with the thickness of 3mm, the cold rolling is carried out for the second time to obtain a strip with the thickness of 1.5mm, the cold rolling is carried out for the third time to obtain a strip with the thickness of 0.7mm, the cold rolling is carried out for the fourth time to obtain a strip with the thickness of 0.3mm, and the annealing temperature in the midway is 950-1150 ℃;
(8) And (5) cold rolling the strip, cleaning, drying, packaging and discharging a finished product.
Alloy finished products prepared in the third to fifth embodiments have high resistivity tensile strength, oxidation resistance and corrosion resistance, overcome the defects of the conventional iron-chromium-aluminum and nickel-chromium alloy material technology, and have high market application value.
The specific test data are as follows:
TABLE 2
Resistivity at room temperature (compare alloys 1, 2, 3 prepared in three-five of the examples with ferrochromium alloy 216 and nichrome alloy 2080, respectively)
TABLE 3
Tensile strength and elongation at various temperatures (example four-alloy 2)
TABLE 4
High temperature oxidation resistance test data, 1200 hours cyclic oxidation experiment
TABLE 5
High temperature oxidation resistance test data: data for oxide increment after 3000 hours of continuous operation in air
According to the test data, the alloy 1, the alloy 2 and the alloy 3 respectively prepared in the third, fourth and fifth embodiments have higher resistivity tensile strength, oxidation resistance and corrosion resistance, overcome the defects in the conventional iron-chromium-aluminum alloy and nickel-chromium alloy material technology, and have higher market application value.
While the embodiment of the present invention provides a high-temperature high-resistance nickel-based alloy and a method for making the same, it will be apparent to those skilled in the art that the concept of the embodiment of the present invention may be modified in the specific implementation and application scope, and in summary, the disclosure of the present invention should not be construed as limiting the scope of the present invention.
Claims (6)
1. The high-temperature high-resistance nickel-based alloy is characterized by comprising the following elements in percentage by mass:
C：0.1-0.3％；Cr：22-25％；Fe:7-10％；Si:<0.5％；Mn:<0.4％；Cu:0.05-0.15％；
Al:2-4.5％；
Ti:0.15-0.45％；Zr:0.05-0.15％；La+Ce+Nb+Y:0.06-0.2％；P:<0.02％；S：<0.01％；B:0.01-0.02％；
and nickel and unavoidable impurities.
2. The method for preparing a high-temperature high-resistance nickel-base alloy according to claim 1, comprising the steps of:
s1, proportioning C, cr, fe, si, mn, cu, al, ti, zr, la, ce, nb, Y, P, S and B according to the element composition and the mass percent;
s2, placing the prepared raw materials into a vacuum induction smelting furnace, smelting, and cooling along with the furnace to form a first alloy ingot;
s3, carrying out electroslag remelting or vacuum self-consumption on the first alloy ingot, purifying metal and carrying out cleaning treatment to obtain a second alloy ingot;
s4, discharging the second alloy ingot out of the furnace, immediately forging the second alloy ingot into a flat blank or a round bar, and performing air cooling treatment;
s5, heating the flat blank or the round bar, preserving heat, taking the blank or the round bar out of the furnace, carrying out hot rolling on the blank or the round bar to obtain a strip or a wire rod, and carrying out air cooling on the hot rolled strip or the wire rod to room temperature;
s6, carrying out acid washing and rinsing on the strip or the wire rod to remove surface oxides;
and S7, carrying out cold rolling or cold drawing and annealing on the strip or wire rod with the surface oxide removed at least twice until the strip or wire rod with the finished thickness is obtained.
3. The method for preparing the high-temperature high-resistance nickel-based alloy according to claim 2, wherein before the raw materials are smelted, the smelting furnace is vacuumized and filled with inert gas for protection.
4. The method for preparing the high-temperature high-resistance nickel-based alloy according to claim 2, wherein before hot rolling, the flat blank or the round bar is heated to 1200-1350 ℃ and is kept warm for 1-3 hours.
5. The method for preparing a high-temperature high-resistance nickel-base alloy according to claim 2, wherein the finishing temperature in the hot rolling is 900 to 1200 ℃.
6. The method for preparing the high-temperature high-resistance nickel-base alloy according to claim 2, wherein the annealing temperature is 950 to 1150 degrees celsius.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116814997A (en) * | 2023-08-30 | 2023-09-29 | 无锡亨通特种合金制造有限公司 | Preparation process of nickel-based alloy |
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| EP0549286A1 (en) * | 1991-12-20 | 1993-06-30 | Inco Alloys Limited | High temperature resistant Ni-Cr alloy |
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| CN111621674A (en) * | 2020-06-08 | 2020-09-04 | 重庆材料研究院有限公司 | Preparation method of microalloyed high-strength precise nickel-chromium resistance alloy material |
| CN112553505A (en) * | 2020-12-25 | 2021-03-26 | 江苏新核合金科技有限公司 | Nickel-based plate and preparation method thereof |
| CN113005333A (en) * | 2021-02-23 | 2021-06-22 | 江苏兄弟合金有限公司 | Ultra-high temperature nickel-based alloy and preparation method thereof |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0549286A1 (en) * | 1991-12-20 | 1993-06-30 | Inco Alloys Limited | High temperature resistant Ni-Cr alloy |
| CN102206773A (en) * | 2011-04-22 | 2011-10-05 | 江苏新华合金电器有限公司 | High-resistance electrothermal alloy material and preparation method thereof |
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Cited By (1)
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| CN116814997A (en) * | 2023-08-30 | 2023-09-29 | 无锡亨通特种合金制造有限公司 | Preparation process of nickel-based alloy |
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