CN118854137B - Si-containing high-entropy alloy material resistant to molten chloride corrosion and preparation method thereof - Google Patents
Si-containing high-entropy alloy material resistant to molten chloride corrosion and preparation method thereof Download PDFInfo
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- CN118854137B CN118854137B CN202411350374.6A CN202411350374A CN118854137B CN 118854137 B CN118854137 B CN 118854137B CN 202411350374 A CN202411350374 A CN 202411350374A CN 118854137 B CN118854137 B CN 118854137B
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- 239000000956 alloy Substances 0.000 title claims abstract description 113
- 238000005260 corrosion Methods 0.000 title claims abstract description 75
- 230000007797 corrosion Effects 0.000 title claims abstract description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 53
- 238000005242 forging Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000005098 hot rolling Methods 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 230000006698 induction Effects 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 11
- 239000010959 steel Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 150000003841 chloride salts Chemical class 0.000 claims description 8
- 239000012856 weighed raw material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 238000010308 vacuum induction melting process Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 150000001804 chlorine Chemical class 0.000 abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 238000003723 Smelting Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 101000912561 Bos taurus Fibrinogen gamma-B chain Proteins 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- -1 nitrate ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910001119 inconels 625 Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
The invention discloses a high-entropy alloy material resisting corrosion of molten chlorine salt and a preparation method thereof, and relates to the technical field of high-entropy alloy materials containing Si, wherein the main components of the high-entropy alloy material comprise, by atomic percentage, 10.0-30.0% of Co, 10.0-30.0% of Cr, 10.0-30.0% of Ni, 6.5-11.0% of Al, 6.5-11.0% of Ti, 1.0-30.0% of Si and the balance of Fe and unavoidable impurities. Compared with the existing alloy material, the Si-containing high-entropy alloy material disclosed by the invention has the advantages of better corrosion resistance to molten chloride, lower material cost, higher high-temperature tissue stability, easiness in processing and easiness in popularization and application.
Description
Technical Field
The invention relates to the technical field of Si-containing high-entropy alloy materials, in particular to a Si-containing high-entropy alloy material resistant to corrosion of molten chloride and a preparation method thereof.
Background
Solar photo-thermal power generation (concentrated solar power, CSP) technology combined with thermal energy storage (hereinafter referred to as heat storage) can efficiently utilize solar energy with abundant resources and intermittence, provides stable, schedulable and low-cost power for people, and is one of the most promising renewable energy technologies in the global scope at present.
At present, nitrate (such as NaNO 3/KNO3) with high thermal stability and low corrosiveness is mainly adopted as a heat storage/heat conduction material in a commercial CSP power station. But above 565 ℃, nitrate ions decompose at a high rate into nitrite ions and oxygen, which limits their use at higher temperatures. To increase thermoelectric efficiency and reduce power generation costs, the operating temperature of next generation CSP power plants may exceed 700 ℃. Compared with the mixed salt of nitrate and carbonate, the mixed salt of chloride has lower cost, higher thermal stability and excellent thermophysical property, and becomes a candidate salt of the most potential next-generation CSP power station.
However, the corrosion of molten chlorine salt is extremely high, and the traditional Cr-containing ferrite steel has poor corrosion resistance of molten chlorine salt, and can not meet the use requirement of the heat exchange tube material of the next-generation CSP power station. Although the high Mo nickel base alloy has better high-temperature molten chlorine salt corrosion resistance, the high Mo nickel base alloy has higher material cost due to the fact that the high Mo nickel base alloy contains a large amount of Mo element with high price. Therefore, there is an urgent need for developing an alloy material for heat exchange tubes of the next-generation CSP power station which has low cost, good high-temperature structure stability and strong resistance to corrosion by molten chloride.
Disclosure of Invention
The invention aims to provide a high-entropy Si-containing alloy material resistant to corrosion of molten chloride and a preparation method thereof, so as to solve the problems in the prior art.
The invention provides a high-entropy alloy material containing Si, which is prepared from (by atomic percentage) Co 10.0-30.0%, cr 10.0-30.0%, ni 10.0-30.0%, al 6.5-11.0%, ti 6.5-11.0%, si 1.0-30.0% and Fe and unavoidable impurities.
Preferably, the composition comprises, by atomic percentage, 15.0-20.0% of Co, 15.0-20.0% of Cr, 15.0-20.0% of Ni, 8.0-10.5% of Al, 8.0-10.5% of Ti, 5.0-25.0% of Si, and the balance of Fe and unavoidable impurities.
A preparation method of a high-entropy alloy material containing Si and resistant to corrosion of molten chloride salt comprises the following steps:
S1, adopting a vacuum induction smelting process, and when raw materials are mixed, mixing the main raw materials according to the following atomic percent (%) by weight, wherein the main raw materials comprise 10.0-30.0% of Co, 10.0-30.0% of Cr, 10.0-30.0% of Ni, 6.5-11.0% of Al, 6.5-11.0% of Ti, 1.0-30.0% of Si, and the balance of Fe and unavoidable impurities. All the weighed raw materials after the proportioning are subjected to vacuum induction smelting to obtain an alloy melt;
S2, casting the alloy melt prepared in the step S1 to form, and sequentially carrying out hot forging, hot rolling and annealing heat treatment on the alloy cast ingot obtained by casting to finally prepare the Si-containing high-entropy alloy material bar or plate resistant to molten chlorine salt corrosion.
Preferably, in the step S1, the raw material components are prepared according to the following atomic percentage composition, namely 15.0-20.0% of Co, 15.0-20.0% of Cr, 15.0-20.0% of Ni, 8.0-10.5% of Al, 8.0-10.5% of Ti, 5.0-25.0% of Si, and the balance of Fe and unavoidable impurities.
Preferably, in the step S1, the weighed raw materials after being mixed are mixed, heated to a temperature of 1500-1600 ℃ according to a temperature rising rate of not lower than 10 ℃ per min, and melted at least 10 min under heat preservation, and the alloy melt is obtained by adopting a vacuum induction melting process.
Preferably, in the step S2, the alloy melt prepared in the step S1 is cast and formed, and the cast alloy ingot is subjected to hot forging, hot rolling and annealing heat treatment in sequence;
wherein, the hot forging temperature is controlled to be 1200-1250 ℃, the hot rolling temperature is controlled to be 1150-1180 ℃, and in order to avoid deformation and cracking in the hot forging and hot rolling processes, the hot forging and hot rolling processes can be performed after multiple times of furnace return for re-forging/rolling;
Finally, the alloy material bar or plate with high entropy of Si and resisting corrosion of molten chloride is prepared by cooling to room temperature after annealing at 1050 ℃ for 30 min ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. Compared with the existing alloy material, the Si-containing high-entropy alloy material with the resistance to corrosion of molten chloride prepared by the method has lower cost.
2. The Si-containing high-entropy alloy material resistant to molten chloride corrosion prepared by the invention can form a continuous SiO 2 film on the surface of the alloy in a molten chloride corrosion environment, the weight change of the alloy material is less than or equal to 5 mg/cm 2 after 700 ℃ molten chloride (NaCl-KCl-MgCl 2, 33-21.6-45.4 and mol%) is corroded for 100 hours, and the corrosion resistance to molten chloride is superior to that of the traditional Cr-containing ferritic steel (T91, 12CrMoV and the like) and high-Mo nickel-based alloy materials (Inconel 625, C22 and the like).
3. After hot forging, hot rolling and annealing treatment, the Si-containing high-entropy alloy material resistant to molten chloride corrosion has excellent mechanical properties, the room-temperature tensile breaking strength is greater than or equal to 950 Mpa, the breaking elongation is greater than or equal to 25%, the defect of easy heat aging of high Mo alloy can be effectively avoided, and the safety of the alloy in the use process can be greatly improved.
Drawings
FIG. 1 is a cross-sectional scan of an alloy material of example one after 100h corrosion with molten chloride at 700 ℃;
FIG. 2 is a graph showing elemental silicon distribution of an alloy material of example one after 100h corrosion of molten chloride at 700 ℃;
FIG. 3 is a graph showing the elemental oxygen distribution of the alloy material of example one after 100h corrosion of molten chlorine salt at 700 ℃.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1 to 3, the present invention provides a technical scheme that the high-entropy alloy material containing Si is resistant to corrosion of molten chloride, and comprises, by atomic percentage, 10.0-30.0% of Co, 10.0-30.0% of Cr, 10.0-30.0% of Ni, 6.5-11.0% of Al, 6.5-11.0% of Ti, 1.0-30.0% of Si, and the balance of Fe and unavoidable impurities.
Preferably, the composition comprises, by atomic percentage, 15.0-20.0% of Co, 15.0-20.0% of Cr, 15.0-20.0% of Ni, 8.0-10.5% of Al, 8.0-10.5% of Ti, 5.0-25.0% of Si, and the balance of Fe and unavoidable impurities.
The functions of the elements in the formula are as follows:
The Co element has the solid solution strengthening function, so that the durability and creep resistance of the alloy are improved, and meanwhile, the solubility of the Al and Ti elements in a matrix is reduced by Co, so that the quantity of gamma 'strengthening phases is increased, and the solid solution temperature of the gamma' phases is also improved along with the addition of Co. In addition, co can improve the hot workability, plasticity and impact toughness of the alloy, and the Co content is preferably 15.0-20.0% in the invention.
Cr element can increase the oxidation resistance and corrosion resistance of the alloy. When the Cr content reaches a critical value (more than 15.0 percent), a layer of continuous, compact and well-adhered Cr 2O3 oxide film is formed on the alloy surface, so that the metal surface can be protected from high-temperature oxidation and thermal corrosion caused by O, cl and the like, and the alloy oxidation corrosion is protected. However, the increase in Cr content tends to enhance the precipitation tendency of the Cr-rich body-centered alpha-Cr phase in the alloy, and the amount of Cr used in the present invention is preferably 15.0 to 20.0%.
The Fe element not only can improve the processing performance of the alloy, but also can reduce the material cost, and the preferable Fe content is 15.0-20.0 percent.
The Ni element has high chemical stability, is hardly oxidized below 500 oC, and can be dissolved in various alloy elements without forming harmful phases, and the Ni is preferably used in an amount of 15.0-20.0%.
The Al and Ti elements are main elements for forming a gamma 'phase, and increasing the total amount of the Al and the Ti can obviously improve the solid solution temperature and the volume fraction of the gamma' phase and improve the mechanical property of the alloy. As the Al and Ti content increases, the size of the gamma 'phase gradually increases, and the morphology of the gamma' phase changes from spherical to cubic and then to irregular. Ti is also MC carbide forming element, forms relatively stable TiC carbide, delays or even prevents carbide reaction at high temperature, so that Cr in a matrix is stable, and indirectly plays a role in hot corrosion resistance. The high Al is beneficial to improving the high-temperature oxidation resistance of the alloy. The preferable Al and Ti elements are 8.0-10.5% respectively.
The addition of Si element can promote the formation of a SiO 2 passivation layer on the surface of the alloy and prevent the dissolution of metal elements in molten chlorine salt. When the content of Si is higher than 1.0%, an Si-rich layer is formed on the surface of the alloy, so that the corrosion resistance of the alloy is improved, when the content of Si is higher than 28.0%, a large-size brittle Si-rich precipitated phase is formed in the alloy, and the structural stability of the alloy is affected, wherein the content of Si is preferably 5.0-25.0%.
A preparation method of a high-entropy alloy material containing Si and resistant to corrosion of molten chloride salt comprises the following steps:
S1, adopting a vacuum induction smelting process, and when raw materials are mixed, mixing the main raw materials according to the following atomic percent (%) by weight, wherein the main raw materials comprise 10.0-30.0% of Co, 10.0-30.0% of Cr, 10.0-30.0% of Ni, 6.5-11.0% of Al, 6.5-11.0% of Ti, 1.0-30.0% of Si, and the balance of Fe and unavoidable impurities. All the weighed raw materials after the proportioning are subjected to vacuum induction smelting to obtain an alloy melt;
S2, casting the alloy melt prepared in the step S1 to form, and sequentially carrying out hot forging, hot rolling and annealing heat treatment on the alloy cast ingot obtained by casting to finally prepare the Si-containing high-entropy alloy material bar or plate resistant to molten chlorine salt corrosion.
Preferably, in the step S1, the raw material components are prepared according to the following atomic percentage composition, namely 15.0-20.0% of Co, 15.0-20.0% of Cr, 15.0-20.0% of Ni, 8.0-10.5% of Al, 8.0-10.5% of Ti, 5.0-25.0% of Si, and the balance of Fe and unavoidable impurities.
Preferably, in the step S1, the weighed raw materials after being mixed are mixed, heated to a temperature of 1500-1600 ℃ according to a temperature rising rate of not lower than 10 ℃ per min, and melted at least 10 min under heat preservation, and the alloy melt is obtained by adopting a vacuum induction melting process.
Preferably, in the step S2, the alloy melt prepared in the step S1 is cast and formed, and the cast alloy ingot is subjected to hot forging, hot rolling and annealing heat treatment in sequence;
wherein, the hot forging temperature is controlled to be 1200-1250 ℃, the hot rolling temperature is controlled to be 1150-1180 ℃, and in order to avoid deformation and cracking in the hot forging and hot rolling processes, the hot forging and hot rolling processes can be performed after multiple times of furnace return for re-forging/rolling;
Finally, the alloy material bar or plate with high entropy of Si and resisting corrosion of molten chloride is prepared by cooling to room temperature after annealing at 1050 ℃ for 30 min ℃.
Embodiment one:
In this embodiment, a high-entropy alloy material containing Si resistant to corrosion by molten chloride and a method for preparing the same, comprising the steps of:
S1, adopting a vacuum induction smelting process, and carrying out raw material proportioning by adopting the following raw material components in percentage by atom:
Co 19.0%;
Cr 19.0%;
Ni 19.0%;
Al 9.5%;
Ti 9.5%;
Si 5.0%;
Fe balance;
Mixing ingredients and the same amount of raw materials, heating to 1500-1600 ℃ according to the heating rate of not lower than 10 ℃ per minute, and carrying out heat preservation smelting to at least 10 min, and obtaining an alloy melt by adopting a vacuum induction smelting process;
S2, casting and forming the alloy melt prepared in the step S1, and sequentially carrying out hot forging, hot rolling and annealing heat treatment on the alloy cast ingot obtained by casting, wherein the hot forging temperature is controlled to be 1200-1250 ℃, the hot rolling temperature is controlled to be 1150-1180 ℃, and in order to avoid deformation and cracking in the hot forging and hot rolling processes, the alloy cast ingot is forged/rolled after being returned to the furnace for multiple times in the thermal deformation process. And finally, annealing at 1050 ℃ for 30min ℃ and cooling to room temperature to obtain the Si-containing high-entropy alloy plate resistant to corrosion of molten chloride.
The test results show that the room-temperature tensile breaking strength of the plate of the Si-containing high-entropy alloy material with the resistance to corrosion by molten chlorine salt prepared in the embodiment is 960 MPa, the breaking elongation is 38%, and the weight change after corrosion by molten chlorine salt at 700 ℃ for 100h is 4.8 mg/cm 2.
1-3 Are cross-sectional scan pictures of an alloy material after molten chlorine salt corrosion at 700 ℃ for 100 hours, and the pictures show that the alloy forms a continuous SiO 2 film on the surface in the molten chlorine salt corrosion process, and the continuous SiO 2 film can prevent the high-temperature molten chlorine corrosion from proceeding, so that the corrosion resistance of the alloy is improved.
The Si-containing high-entropy alloy material with the resistance to molten chloride corrosion prepared by the embodiment has excellent mechanical properties, and the resistance to molten chloride corrosion is superior to that of the traditional Cr-containing ferritic steel or high-Mo nickel-based alloy material, so that the alloy material can be used as a part of a next-generation CSP power station heat exchange tube material and the like, is an optimal candidate material for replacing the traditional Cr-containing ferritic steel or high-Mo nickel-based material and the like in the future, and can greatly improve the resistance to molten chloride corrosion and safety.
Embodiment two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
In this embodiment, a preparation method of a high-entropy alloy material with excellent mechanical properties and resistance to corrosion of molten chloride salt, which comprises the following steps:
s1, adopting a vacuum induction smelting process, and carrying out raw material proportioning by adopting raw material components according to the following mass percent (%):
Co 18.0%;
Cr 18.0%;
Ni 18.0%;
Al 9.0%;
Ti 9.0%;
Si 10.0%;
Fe balance;
All the weighed raw materials after the proportioning are subjected to vacuum induction smelting to obtain an alloy melt;
S2, the step is the same as that of the first embodiment.
The test results show that the room-temperature tensile breaking strength of the plate of the Si-containing high-entropy alloy material resistant to molten chloride corrosion prepared by the embodiment is 980 MPa, the breaking elongation is 31%, the weight change of the plate after molten chloride corrosion at 700 ℃ for 100h is 4.3 mg/cm 2, and a continuous SiO 2 film is formed on the surface of the alloy in the molten chloride corrosion process. The Si-containing high-entropy alloy material with the resistance to molten chloride corrosion prepared by the embodiment has excellent mechanical properties, and the resistance to molten chloride corrosion is superior to that of the traditional Cr-containing ferritic steel or high-Mo nickel-based alloy material, so that the alloy material can be used as a part of a next-generation CSP power station heat exchange tube material and the like, is an optimal candidate material for replacing the traditional Cr-containing ferritic steel or high-Mo nickel-based material and the like in the future, and can greatly improve the resistance to molten chloride corrosion and safety.
Embodiment III:
This embodiment is substantially identical to the previous embodiment, except that:
In this embodiment, a preparation method of a high-entropy alloy material with excellent mechanical properties and resistance to corrosion of molten chloride salt, which comprises the following steps:
s1, adopting a vacuum induction smelting process, and carrying out raw material proportioning by adopting raw material components according to the following mass percent (%):
Co 17.0%;
Cr 17.0%;
Ni 17.0%;
Al 8.5%;
Ti 8.5%;
Si 15.0%;
Fe balance;
All the weighed raw materials after the proportioning are subjected to vacuum induction smelting to obtain an alloy melt;
S2, the step is the same as that of the first embodiment.
The test results show that the room-temperature tensile breaking strength of the plate of the Si-containing high-entropy alloy material resistant to molten chloride corrosion prepared by the embodiment is 1050 MPa, the breaking elongation is 28%, the weight change of the plate after molten chloride corrosion at 700 ℃ for 100h is 3.2 mg/cm 2, and a continuous SiO 2 film is formed on the surface of the alloy in the molten chloride corrosion process. The Si-containing high-entropy alloy material with the resistance to molten chloride corrosion prepared by the embodiment has excellent mechanical properties, and the resistance to molten chloride corrosion is superior to that of the traditional Cr-containing ferritic steel or high-Mo nickel-based alloy material, so that the alloy material can be used as a part of a next-generation CSP power station heat exchange tube material and the like, is an optimal candidate material for replacing the traditional Cr-containing ferritic steel or high-Mo nickel-based material and the like in the future, and can greatly improve the resistance to molten chloride corrosion and safety.
Embodiment four:
This embodiment is substantially identical to the previous embodiment, except that:
In this embodiment, a preparation method of a high-entropy alloy material with excellent mechanical properties and resistance to corrosion of molten chloride salt, which comprises the following steps:
s1, adopting a vacuum induction smelting process, and carrying out raw material proportioning by adopting raw material components according to the following mass percent (%):
Co 16.0%;
Cr 16.0%;
Ni 16.0%;
Al 8.0%;
Ti 8.0%;
Si 20.0%;
Fe balance;
All the weighed raw materials after the proportioning are subjected to vacuum induction smelting to obtain an alloy melt;
S2, the step is the same as that of the first embodiment.
The test results show that the room-temperature tensile breaking strength of the plate of the Si-containing high-entropy alloy material resistant to molten chloride corrosion prepared by the embodiment is 1080 MPa, the breaking elongation is 26%, the weight change of the plate after molten chloride corrosion at 700 ℃ for 100h is 2.9 mg/cm 2, and a continuous SiO 2 film is formed on the surface of the alloy in the molten chloride corrosion process. The Si-containing high-entropy alloy material with the resistance to molten chloride corrosion prepared by the embodiment has excellent mechanical properties, and the resistance to molten chloride corrosion is superior to that of the traditional Cr-containing ferritic steel or high-Mo nickel-based alloy material, so that the alloy material can be used as a part of a next-generation CSP power station heat exchange tube material and the like, is an optimal candidate material for replacing the traditional Cr-containing ferritic steel or high-Mo nickel-based material and the like in the future, and can greatly improve the resistance to molten chloride corrosion and safety.
In summary, the Si-containing high-entropy alloy material resistant to corrosion by high-temperature molten chlorine salt has excellent mechanical properties and high-temperature molten chlorine salt corrosion resistance, and comprises, by atomic percent (%), 10.0-30.0% of Co, 10.0-30.0% of Cr, 10.0-30.0% of Ni, 6.5-11.0% of Al, 6.5-11.0% of Ti, 1-30% of Si, and the balance of Fe and unavoidable impurities. The alloy material bar or plate with excellent mechanical property and high temperature resistance to corrosion of chloridion molten salt is finally prepared through the processes of proportioning, vacuum induction melting, casting molding, hot forging, hot rolling, annealing treatment and the like. The alloy material resistant to high-temperature chloride ion molten salt corrosion has the advantages of good strong plasticity, high tissue stability, low cost, good chloride ion corrosion resistance, good hot forming property and the like
It will be appreciated by those skilled in the art that the present invention can be carried out in other embodiments without departing from the spirit or essential characteristics thereof. Accordingly, the above disclosed embodiments are illustrative in all respects, and not exclusive. All changes that come within the scope of the invention or equivalents thereto are intended to be embraced therein.
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