CN111088448A - Cobalt-based high-temperature alloy strip foil and preparation method thereof - Google Patents
Cobalt-based high-temperature alloy strip foil and preparation method thereof Download PDFInfo
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- CN111088448A CN111088448A CN201911360570.0A CN201911360570A CN111088448A CN 111088448 A CN111088448 A CN 111088448A CN 201911360570 A CN201911360570 A CN 201911360570A CN 111088448 A CN111088448 A CN 111088448A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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Abstract
A cobalt-based high-temperature alloy foil and a preparation method thereof belong to the technical field of metal rolling processing. The alloy comprises the following components in percentage by mass: 0.05-0.15%, Cr: 19.0% -21.0%, Ni: 9.0-11.0%, Mn: 1.0% -2.0%, W: 14.0% -16.0%, Fe: less than or equal to 3 percent, Mo: 0.2% -1.0%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co. The alloy is subjected to vacuum and electroslag smelting, conventional forging, hot rolling and cold rolling, the cold rolling intermediate annealing temperature is 1150-1230 ℃, and the heat preservation time is 1-5 minutes; annealing at 850-1080 ℃ after cold rolling of the finished product, and keeping the temperature for 1-5 minutes; the cold rolling deformation of the intermediate and finished products is controlled to be 15-45 percent; the cold rolling intermediate and the finished product annealing are carried out in a bright continuous annealing furnace protected by pure hydrogen. The method has the advantage that the high-strength high-plasticity alloy foil with good obdurability matching is obtained.
Description
Technical Field
The invention belongs to the technical field of metal rolling processing, and particularly relates to a preparation method of a cobalt-based high-temperature alloy strip foil.
Background
The CoNiCrW alloy is a cobalt-based high-temperature alloy which is solid solution strengthened by 20 percent of Cr and 15 percent of W, has excellent hot corrosion resistance, has moderate endurance and creep strength at the temperature of below 815 ℃, good wear resistance, satisfactory technological properties such as forming and welding and the like, and becomes one of the cobalt-based wrought high-temperature alloys which are most widely applied at home and abroad at present. However, the conventional production uses the foil which is in a solid solution state after high-temperature solid solution treatment, has good plasticity and high-temperature durability, but has lower strength. In particular, an alloy foil with high strength and good plasticity is urgently needed in some application fields.
At present, the conventional production of the CoNiCrW alloy uses a strip foil in a solid solution state, and high-temperature annealing is carried out at the temperature of 1180-1230 ℃ after cold rolling, so that the tensile strength at room temperature cannot meet the requirement of high strength and high plasticity in a certain specific field. Therefore, it is necessary to find a method for processing a strip foil having high strength and good plasticity.
Disclosure of Invention
The invention aims to provide a cobalt-based high-temperature alloy foil and a preparation method thereof, and the cobalt-based high-temperature alloy foil with high strength and high plasticity is obtained, and compared with the conventional produced foil, the tensile yield strength at room temperature is higher by more than 80%, and meanwhile, the tensile elongation at room temperature is still not less than 20%.
The cobalt-based high-temperature alloy strip foil comprises the following components in percentage by mass: 0.05-0.15%, Cr: 19.0% -21.0%, Ni: 9.0-11.0%, Mn: 1.0% -2.0%, W: 14.0% -16.0%, Fe: less than or equal to 3 percent, Mo: 0.2% -1.0%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co.
The cobalt-based high-temperature alloy strip foil is subjected to vacuum and electroslag smelting, conventional forging, hot rolling and cold rolling, wherein the cold rolling intermediate annealing temperature is 1150-1230 ℃, and the heat preservation time is 1-5 minutes; annealing at 850-1080 ℃ after cold rolling of the finished product, and keeping the temperature for 1-5 minutes; the cold rolling deformation of the intermediate and finished products is controlled to be 15-45 percent; and (3) annealing the cold rolling intermediate and finished products in a bright continuous annealing furnace protected by pure hydrogen to obtain the high-strength high-plasticity alloy strip foil with good obdurability matching.
The preparation method of the cobalt-based high-temperature alloy strip foil comprises the following steps of:
(1) alloy smelting: according to the components and mass percentage of the alloy as C: 0.05-0.15%, Cr: 19.0% -21.0%, Ni: 9.0-11.0%, Mn: 1.0% -2.0%, W: 14.0% -16.0%, Fe: less than or equal to 3 percent, Mo: 0.2% -1.0%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co, putting the raw materials into a vacuum induction melting furnace for melting, and pouring electrodes; carrying out secondary smelting in an electroslag furnace to obtain an alloy ingot;
(2) hot processing: forging and hot rolling the alloy ingot obtained by smelting to obtain a strip billet;
(3) grinding: carrying out grinding and finishing on the belt blank by using a grinding wheel or a grinding belt;
(4) cold rolling: carrying out multiple-pass cold rolling cogging and finish rolling finished products accompanied with intermediate annealing on the strip blank in a multi-roll cold rolling mill; the deformation of the intermediate and finished products is controlled to be 15-45 percent; the intermediate annealing is carried out in a bright continuous annealing furnace protected by pure hydrogen, the annealing temperature is 1150-1230 ℃, and the heat preservation time is 1-5 minutes;
(5) annealing of a finished product: and annealing the finished product with the foil in a hydrogen-protected bright continuous annealing furnace at the annealing temperature of 850-1080 ℃ for 1-5 minutes.
The invention further controls the mass percent of the alloy components C: 0.08-0.12%, Cr: 19.0% -20.0%, Ni: 10.0% -10.6%, W: 14.5-15.5%, Mn: 1.0% -2.0%, Fe: 1.5% -2.8%, Mo: 0.2-0.8%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co.
Further, the strip is subjected to multiple-rolling-process cold rolling cogging accompanied with intermediate annealing and finished products of finish rolling in a multi-roll cold rolling mill; the deformation of the intermediate and finished products is controlled to be 20-40 percent.
Further, the cobalt-based high-temperature alloy strip foil cold rolling intermediate annealing temperature is 1160-1200 ℃, and the heat preservation time is 1-5 minutes.
Further, the annealing temperature of the cobalt-based high-temperature alloy foil finished product is 850-1000 ℃, and the heat preservation time is 1-5 minutes.
The technical principle of the invention is as follows:
the C element is a solid solution strengthening element and is an important carbide forming element, the carbide plays an important strengthening role in the deformed cobalt-based high-temperature alloy and also plays an important role in the structure control of the alloy, and the retention of a certain amount of carbide is a necessary condition for ensuring the alloy strength, tests prove that the alloy C content is below 0.07 percent, the alloy strength is obviously reduced, and a large amount of carbide is easily formed due to overhigh carbon content, which is unfavorable for the processing and preparation of the alloy, and through experimental research, the C content range of the alloy is preferably 0.08-0.12 percent; cr is an essential element for ensuring the oxidation resistance and the corrosion resistance of the alloy, and is also a solid solution strengthening element and a carbide forming element, but Cr is an element for promoting HCP phase transformation of the cobalt-based alloy, so the content range of the Cr element is preferably 19-20 percent; w is an important solid solution strengthening element and carbide forming element and is an element for promoting HCP phase transformation of the cobalt-base alloy, and the content range of the W element is preferably 14.5-15.5 percent; mo is an important solid solution strengthening element and carbide forming element and is an element for promoting HCP phase transformation of the cobalt-based alloy, and the content range of the Mo element is increased and preferably ranges from 0.2% to 0.8% on the basis of the original CoNiCrW alloy; ni is an effective stable austenite element in the cobalt-based alloy, and the content of the Ni element is preferably 10.0-10.6 percent; an excessively high Fe element promotes the formation of a harmful phase in the co-based alloy, but a small amount of Fe stabilizes the austenite matrix, and thus the Fe element content is preferably in the range of 1.5 to 2.8% in the present invention.
The invention relates to an alloy strip foil which is in a solid solution state in the traditional use state, namely, the alloy foil is annealed at 1180-1230 ℃ after cold rolling and subjected to high-temperature solid solution, the alloy has larger crystal grains and few carbides, and the tensile strength at room temperature cannot meet the high-strength requirement of a specific field. The invention adopts higher annealing temperature to anneal in the cold-processing cogging stage of the alloy foil, dissolves out large carbides, obtains more uniform structure and controls the grain structure with proper size, obtains high plasticity, ensures the good rolling forming of the foil, and adopts relatively low temperature annealing after cold rolling finished products to obtain alloy structure strengthened by fine grains and fine dispersion carbides, thereby obtaining good matching of high plasticity and high strength.
Compared with the prior art, the invention has the following advantages:
1) aiming at specific application, the method carries out component optimization and process adjustment on the basis of the traditional cobalt-based high-temperature alloy, and prepares a novel high-strength high-plasticity cobalt-based high-temperature alloy strip foil.
2) The high-strength high-plasticity cobalt-based high-temperature alloy foil is not lower than 900MPa in tensile yield strength at room temperature and not lower than 1300MPa in tensile strength, the tensile yield strength at room temperature is higher than 80% of that of the conventional produced foil, and meanwhile, the tensile elongation at room temperature is still not lower than 20%.
Detailed Description
The technical scheme of the invention is further illustrated by the following examples.
Comparative example 1: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Preparing the cobalt-based high-temperature alloy strip according to a traditional preparation method. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing, finally cold rolling the strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then carrying out solid solution treatment. The cold rolling intermediate annealing and finished product annealing treatment is 1190 ℃/5 minutes bright continuous annealing. The cold rolling cogging deformation is 35%, and the cold rolling finished product deformation is 35%.
Comparative example 2: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1170 ℃/5 min bright continuous annealing, and the finished product annealing treatment is 900 ℃/5 min bright continuous annealing. The cold rolling cogging deformation is 35%, and the cold rolling finished product deformation is 35%.
Example 1: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1170 ℃/5 min bright continuous annealing, and the finished product annealing treatment is 900 ℃/5 min bright continuous annealing. The cold rolling cogging deformation is 35%, and the cold rolling finished product deformation is 35%.
Example 2: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1180 ℃/3 minutes of bright continuous annealing, and the finished product annealing treatment is 1080 ℃/2 minutes of bright continuous annealing. The cold rolling cogging deformation is 25 percent, and the deformation of the cold rolling finished product is 15 percent.
Example 3: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1170 ℃/2 min bright continuous annealing, and the finished product annealing treatment is 870 ℃/5 min bright continuous annealing. The cold rolling cogging deformation is 15%, and the cold rolling finished product deformation is 35%.
Example 4: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1230 ℃/1 minute bright continuous annealing, and the finished product annealing treatment is 920 ℃/5 minutes bright continuous annealing. The cold rolling cogging deformation is 45%, and the cold rolling finished product deformation is 45%.
Example five: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1150 ℃/5 min bright continuous annealing, and the finished product annealing treatment is 850 ℃/5 min bright continuous annealing. The cold rolling cogging deformation is 30 percent, and the cold rolling finished product deformation is 30 percent.
Example six: the compositions of the alloys tested and their room temperature tensile properties are shown in Table 1. Forging and hot rolling the ingot after vacuum induction and electroslag remelting to form a strip blank with the thickness of 5mm, polishing the strip blank, finally cold rolling the polished strip blank to a strip product with the thickness of 0.5mm through multiple rolling passes of intermediate annealing, and then annealing. The cold rolling intermediate annealing system is 1190 ℃/2 min bright continuous annealing, and the finished product annealing treatment is 1000 ℃/1 min bright continuous annealing. The cold rolling cogging deformation is 40 percent, and the cold rolling finished product deformation is 20 percent.
TABLE 1 comparative and examples chemical composition and tensile Properties at Room temperature
The method for preparing the cobalt-based high-temperature alloy foil with high strength and high plasticity is not limited to the embodiments. It should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Variations or modifications in other variations may occur to those skilled in the art based upon the foregoing description. And are neither required nor exhaustive of all embodiments. And such obvious modifications or variations that fall within the spirit of the invention are intended to be included within the scope of the invention.
Claims (6)
1. A high-strength high-plasticity cobalt-based high-temperature alloy foil is characterized by comprising the following components in percentage by mass: c: 0.05-0.15%, Cr: 19.0% -21.0%, Ni: 9.0-11.0%, Mn: 1.0% -2.0%, W: 14.0% -16.0%, Fe: less than or equal to 3 percent, Mo: 0.2% -1.0%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co;
the alloy is subjected to vacuum and electroslag smelting, conventional forging, hot rolling and cold rolling, the cold rolling intermediate annealing temperature is 1150-1230 ℃, and the heat preservation time is 1-5 minutes; annealing at 850-1080 ℃ after cold rolling of the finished product, and keeping the temperature for 1-5 minutes; the cold rolling deformation of the intermediate and finished products is controlled to be 15-45 percent; and (3) annealing the cold rolling intermediate and finished products in a bright continuous annealing furnace protected by pure hydrogen to obtain the high-strength high-plasticity alloy strip foil with good obdurability matching.
2. The high-strength high-plasticity cobalt-based high-temperature alloy strip foil as claimed in claim 1, wherein the high-strength high-plasticity cobalt-based high-temperature alloy strip foil comprises the following components in percentage by mass: c: 0.08-0.12%, Cr: 19.0% -20.0%, Ni: 10.0% -10.6%, W: 14.5-15.5%, Mn: 1.0% -2.0%, Fe: 1.5% -2.8%, Mo: 0.2-0.8%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co.
3. The preparation method of the high-strength high-plasticity cobalt-based high-temperature alloy strip foil as claimed in claim 1, wherein the method comprises the following steps:
(1) alloy smelting: according to the components and mass percentage of the alloy as C: 0.05-0.15%, Cr: 19.0% -21.0%, Ni: 9.0-11.0%, Mn: 1.0% -2.0%, W: 14.0% -16.0%, Fe: less than or equal to 3 percent, Mo: 0.2% -1.0%, Si: less than or equal to 0.40 percent, P: less than or equal to 0.04 percent, less than or equal to 0.03 percent of S and the balance of Co, putting the raw materials into a vacuum induction melting furnace for melting, and pouring electrodes; carrying out secondary smelting in an electroslag furnace to obtain an alloy ingot;
(2) hot processing: forging and hot rolling the alloy ingot obtained by smelting to obtain a strip billet;
(3) grinding: carrying out grinding and finishing on the belt blank by using a grinding wheel or a grinding belt;
(4) cold rolling: carrying out multiple-pass cold rolling cogging and finish rolling finished products accompanied with intermediate annealing on the strip blank in a multi-roll cold rolling mill; the deformation of the intermediate and finished products is controlled to be 15-45 percent; the intermediate annealing is carried out in a bright continuous annealing furnace protected by pure hydrogen, the annealing temperature is 1150-1230 ℃, and the heat preservation time is 1-5 minutes;
(5) annealing of a finished product: and annealing the finished product with the foil in a hydrogen-protected bright continuous annealing furnace at the annealing temperature of 850-1080 ℃ for 1-5 minutes.
4. The method of claim 3, wherein: carrying out multiple-pass cold rolling cogging and finish rolling finished products accompanied with intermediate annealing on the strip blank in a multi-roll cold rolling mill; the deformation of the intermediate and finished products is controlled to be 20-40 percent.
5. The method of claim 3, wherein: the cold rolling intermediate annealing temperature of the cobalt-based high-temperature alloy strip foil is 1160-1200 ℃, and the heat preservation time is 1-5 minutes.
6. The method of claim 3, wherein: annealing temperature of the cobalt-based high-temperature alloy foil finished product is 850-1000 ℃, and heat preservation time is 1-5 minutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111304566A (en) * | 2020-03-06 | 2020-06-19 | 东北特殊钢集团股份有限公司 | Heat treatment method of hard GH5605 high-temperature alloy cold-rolled strip |
| CN111850349A (en) * | 2020-07-30 | 2020-10-30 | 北京北冶功能材料有限公司 | Hot processing method of cobalt-based high-temperature alloy |
| CN112342441A (en) * | 2020-11-07 | 2021-02-09 | 南京聚力化工机械有限公司 | High-wear-resistance alloy material and preparation method thereof |
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| CN111304566A (en) * | 2020-03-06 | 2020-06-19 | 东北特殊钢集团股份有限公司 | Heat treatment method of hard GH5605 high-temperature alloy cold-rolled strip |
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