CN113528924A - Nickel-niobium-chromium intermediate alloy and preparation method thereof - Google Patents
Nickel-niobium-chromium intermediate alloy and preparation method thereof Download PDFInfo
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- CN113528924A CN113528924A CN202110837197.4A CN202110837197A CN113528924A CN 113528924 A CN113528924 A CN 113528924A CN 202110837197 A CN202110837197 A CN 202110837197A CN 113528924 A CN113528924 A CN 113528924A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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Abstract
The invention discloses a nickel-niobium-chromium intermediate alloy which comprises the following components in percentage by mass: 36.0 to 41.0 percent of niobium, 16.0 to 21.0 percent of chromium, and the balance of nickel and inevitable impurities; the preparation method comprises the following steps: (1) mixing a niobium source, a chromium source and aluminum, and carrying out aluminothermic reaction to obtain a niobium-chromium alloy; (2) mixing the niobium-chromium alloy and electrolytic nickel, and carrying out vacuum induction smelting to obtain a nickel-niobium-chromium alloy solution; (3) and cooling the nickel-niobium-chromium alloy liquid to obtain the nickel-niobium-chromium alloy. The invention controls the components and the content, so that the nickel-niobium-chromium intermediate alloy has uniform components, small segregation and low gas impurity content, and is beneficial to homogenizing the components of the high-temperature alloy, preventing the component segregation, reducing the element burning loss and improving the quality of the high-temperature alloy when the high-temperature alloy is smelted.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a nickel-niobium-chromium intermediate alloy and a preparation method thereof.
Background
The high-temperature alloy is an alloy which takes iron, nickel and cobalt as bases, is in service in a high-temperature environment, can bear severe mechanical stress and has good surface stability. The high-temperature alloy generally has high room temperature and high temperature strength, good oxidation resistance and hot corrosion resistance, excellent creep deformation and fatigue resistance, good structural stability and use reliability, so the high-temperature alloy is not only a key material of high-temperature parts of aviation and aerospace engines, but also an indispensable important material in industrial fields of ships, energy sources, petrochemical industry and the like.
The nickel-based high-temperature alloy is a high-temperature alloy which takes nickel as a matrix (the content is generally more than 50 percent), has higher strength and good oxidation resistance and fuel gas corrosion resistance within the range of 650-1000 ℃, and is formed by Cr20Ni80Developed on the basis of the alloy, in order to meet the requirements of high-temperature heat strength at about 1000 ℃ and oxidation resistance and corrosion resistance in a gas medium, a large amount of strengthening elements such as W, Mo, Nb, Cr and the like are added. In the whole field of high-temperature alloys, nickel-based high-temperature alloys take a special important position. Compared with iron-based and cobalt-based high-temperature alloys, the nickel-based high-temperature alloy has higher high-temperature strength and structural stability, and is widely applied to manufacturing hot end components of aviation jet engines and industrial gas turbines.
The electrolytic nickel has a melting point of 1453.0 deg.C and a density of 8.90g/cm3The melting point of the metal niobium is 2468 ℃ and the density is 8.57g/cm3The melting point of the metallic chromium is 1857 ℃, and the density is 7.19g/cm3. When a metal is added directly as a simple substance in the production of a high-temperature alloy, the element is easily burned due to a difference in melting point and density, and the refractory element is easily segregated. Of metallic nickel at the same timeThe price is high, the method is not suitable for batch production, meanwhile, the smelting temperature is high, the preparation process is complex, the requirement on equipment in the industrial production process is high, and further, the production cost is increased.
Therefore, how to develop a nickel niobium chromium intermediate alloy to improve the comprehensive performance of the nickel-based superalloy is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a nickel-niobium-chromium intermediate alloy and a preparation method thereof, so as to solve the above problems in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nickel-niobium-chromium intermediate alloy comprises the following components in percentage by mass: 36.0 to 41.0 percent of niobium, 16.0 to 21.0 percent of chromium, and the balance of nickel and inevitable impurities;
preferably: 37.0 to 40.0 percent of niobium, 17.0 to 20.0 percent of chromium, and the balance of nickel and inevitable impurities;
more preferably: 38.5% of niobium, 18.5% of chromium, the balance of nickel and inevitable impurities.
The nickel-niobium-chromium intermediate alloy has the beneficial effects that: niobium is added to improve the plasticity and toughness of the high-temperature alloy; the high-temperature alloy has high strength and good plasticity by adding chromium and can be strengthened by heat treatment; the nickel is added to neutralize the melting point difference and the density difference between the nickel matrix and the niobium-chromium, which is beneficial to the smelting of the final nickel-based high-temperature alloy.
According to the invention, the components are prepared into the intermediate alloy through controlling the components and the content, the melting point difference and the density difference among the elements are neutralized, meanwhile, the density and the melting point of the intermediate alloy are closer to the density and the melting point of a nickel matrix, the problems of element burning loss caused by the melting point difference, component unevenness caused by the density difference and the like in the high-temperature alloy smelting process are avoided, the nickel-niobium-chromium intermediate alloy has uniform components, small segregation and low gas impurity content, and when the high-temperature alloy is smelted, the components of the high-temperature alloy are homogenized, the component segregation is prevented, the element burning loss is reduced, and the quality of the high-temperature alloy is improved.
A preparation method of a nickel-niobium-chromium intermediate alloy specifically comprises the following steps:
(1) mixing a niobium source, a chromium source and aluminum, and carrying out aluminothermic reaction to obtain a niobium-chromium alloy;
(2) mixing the niobium-chromium alloy and electrolytic nickel, and carrying out vacuum induction smelting to obtain a nickel-niobium-chromium alloy solution;
(3) and cooling the nickel-niobium-chromium alloy liquid to obtain the nickel-niobium-chromium intermediate alloy.
The preparation method has the beneficial effects that: the melting point of the niobium-chromium alloy smelted in the first step is about 1650 ℃, electrolytic nickel is added in the second step, so that the melting point of the obtained nickel-niobium-chromium intermediate alloy is close to the melting point of metallic nickel, the melting point difference and the density difference of three metals of nickel, niobium and chromium are neutralized, when the nickel-niobium-chromium intermediate alloy is used for smelting high-temperature alloy, the element burning loss rate is low, and the smelted high-temperature alloy has uniform components and no segregation.
Further, in the step (1), before the niobium source, the chromium source and the aluminum are mixed, the niobium source, the chromium source and the aluminum are respectively dried; in the step (2), before the niobium-chromium alloy and the electrolytic nickel are mixed, respectively drying the niobium-chromium alloy and the electrolytic nickel; furthermore, the drying temperature is 118-122 ℃, preferably 120 ℃, and the drying time is more than or equal to 12 hours. The invention has no special requirements on the mixing process, and the process well known in the field can ensure that all the raw materials are uniformly mixed. In the specific embodiment of the present invention, the mixing is preferably carried out in a V-blender, and there is no particular requirement for other conditions of mixing. In the invention, the mixing can ensure that all components are fully contacted, thereby facilitating the subsequent thermite reaction.
The method has the further beneficial effects that the drying treatment can remove moisture absorbed by the materials and ensure the drying of the materials, so that the impurity gas such as hydrogen, nitrogen, oxygen and the like separated out in the smelting process is reduced; the time is more than or equal to 12 hours to ensure the complete drying of the materials, the materials cannot be completely dried if the time is too short, and resources are wasted if the time is too long.
Further, in the step (1), the niobium source is niobium pentoxide, and the purity is preferably more than or equal to 99.80%; the chromium source is chromium oxide, and the purity is preferably more than or equal to 99.30 percent; the purity of the aluminum is preferably more than or equal to 99.80 percent; and the niobium source, the chromium source and the aluminum are preferably powders. Furthermore, the mass ratio of the niobium pentoxide to the chromium oxide to the aluminum is (1.82-2.08): (0.82-1.09): (0.99-1.01).
The niobium-chromium alloy has the further beneficial effects that the mass ratio of niobium to chromium in the niobium-chromium alloy is controlled by controlling the mass ratio of the niobium source, the chromium source and aluminum.
Further, in the step (1), the temperature of the aluminothermic reaction is 1850-1950 ℃, preferably 1880-1920 ℃; the time is 35-45s, preferably 46-49 s. The reaction device for the thermite reaction is not particularly limited, and can be prepared by adopting a thermite reaction device well known in the art, preferably prepared from graphite, magnesia brick or corundum, more preferably prepared from corundum, so that other elements are not introduced, and the thermite reaction device can be recycled. The ignition mode for initiating the thermite reaction is not particularly limited in the present invention, and may be any mode known in the art. After the thermite reaction is finished, the obtained niobium-chromium alloy liquid is preferably cooled, the cooling mode is preferably furnace cooling, and the cooling time is preferably 12 hours. After cooling, the niobium-chromium alloy ingot obtained by cooling is preferably subjected to finishing crushing and selection in sequence, the method for finishing crushing is not particularly limited, and the niobium-chromium alloy ingot obtained by cooling is subjected to finishing crushing to blocks of 5-50mm by adopting a method well known in the art; the selection preferably comprises magnetic separation and manual selection, magnetic impurities, oxide-containing films, nitride film alloys and other impurities are selected, and qualified parts are selected as the niobium-chromium alloy.
The method has the further beneficial effects that in the aluminothermic reaction process, aluminum is used as a reducing agent, a niobium source (niobium pentoxide) and a chromium source (chromium sesquioxide) are respectively reduced into elemental metal niobium and elemental metal chromium, aluminum is oxidized into aluminum oxide, and a large amount of heat energy is released to melt the elemental metal niobium and the elemental metal chromium to form the niobium-chromium alloy liquid; and aluminum oxide formed by oxidizing aluminum floats on the surface of the niobium-chromium alloy liquid, and is naturally separated from the niobium-chromium alloy and removed after being cooled.
Further, in the step (2), the mass ratio of the niobium-chromium alloy to the electrolytic nickel is (1.32-1.33): (0.99-1.01), preferably 1.326: 1; furthermore, the shape of the electrolytic nickel is preferably blocky, and the purity is preferably more than or equal to 99.00 percent. The mixing process is not particularly limited in the present invention, and the raw materials can be uniformly mixed by selecting a process known to those skilled in the art.
Further, in the step (2), the vacuum induction melting comprises melting and refining which are sequentially carried out; furthermore, the vacuum degree of vacuum induction melting is less than or equal to 10 Pa; the refining power is 100kW, the temperature is 1850-1900 ℃, preferably 1850 ℃, and the time is 5-10min, preferably 6-8 min. The vacuum induction melting is preferably carried out in a medium-frequency vacuum induction furnace, and the crucible for vacuum induction melting is preferably a corundum crucible, namely: placing the niobium-chromium alloy and the electrolytic nickel in a corundum crucible, and then placing the corundum crucible in a medium-frequency vacuum induction furnace for vacuum induction smelting. In the invention, in order to control the content of impurity elements in the alloy, the purity of the corundum crucible is preferably more than or equal to 99.00 percent; the furnace lining for the corundum crucible knotting is preferably prepared by adopting the aluminothermic slag (alumina), so that reaction raw materials are fully utilized, and the cost is saved; the preparation method of the furnace lining for knotting the corundum crucible has no special requirement, and the method well known in the field can be adopted. The invention preferably melts the niobium-chromium alloy and the electrolytic nickel by slowly increasing the heating power of the vacuum induction melting, and refines after the niobium-chromium alloy and the electrolytic nickel are completely melted. In the invention, the smelting power is preferably adjusted according to the melting degree of the alloy, in the invention, the vacuum induction smelting process is preferably carried out by adjusting the initial power to 20kW, adjusting the power to 30kW after 10min, adjusting the power to 80kW after 20min until the alloy is completely melted, finally adjusting the power to 100kW for refining, reducing the power to 80kW and starting casting.
The medium-frequency vacuum induction melting furnace has the further beneficial effects of high thermal efficiency, quick melting, difficult introduction of impurities due to vacuum operation and small environmental pollution. The refining can ensure that the nickel-niobium-chromium intermediate alloy is more fully and uniformly melted, plays a role in purifying and removing impurities, and can ensure that the refining temperature is slightly higher than the melting point of the alloy by controlling the temperature so as to achieve the refining purpose. By controlling the degree of vacuum, the content of O, N gas phase impurities in the finally prepared master alloy can be reduced.
Further, in the step (3), after the refining is completed, the nickel-niobium-chromium alloy liquid obtained by vacuum induction melting is preferably poured into a water-cooled copper crucible for cooling, so as to obtain the nickel-niobium-chromium intermediate alloy. The cooling is preferably carried out under vacuum, the cooling time preferably being ≥ 12 h. The water-cooled copper crucible of the present invention is not particularly limited, and a water-cooled copper crucible known in the art may be used.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the invention adopts a two-step method to prepare the nickel-niobium-chromium intermediate alloy, namely the two steps of thermite reaction and vacuum induction melting: firstly preparing the niobium-chromium alloy by an aluminothermic process, then carrying out vacuum induction smelting, and adding electrolytic nickel to adjust the alloy components by taking the niobium-chromium alloy as a matrix during the vacuum induction smelting so as to enable the components of the target alloy to be more stable. The preparation method provided by the invention can improve the uniform stability of the components of the nickel-niobium-chromium intermediate alloy, reduce element burning loss, has low gas impurity content, and better meets the production requirements of high-temperature alloys.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the nickel-niobium-chromium intermediate alloy specifically comprises the following steps:
(1) firstly, respectively drying niobium pentoxide, chromium trioxide and aluminum powder at the temperature of 118 ℃ for 12 hours, then weighing 90.33kg of niobium pentoxide, 53.84kg of chromium trioxide and 49.69kg of aluminum powder, putting the weighed materials into a V-shaped mixer, fully mixing the materials uniformly, putting the uniformly mixed furnace burden into a sintered corundum crucible for ignition reaction at the temperature of 1950 ℃ for 45 seconds, cooling the mixture for 12 hours, removing the crucible, taking out an alloy ingot, removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing the alloy ingot to 5-50mm, and carrying out magnetic separation and manual selection to obtain the niobium-chromium alloy;
(2) firstly, respectively drying niobium-chromium alloy and electrolytic nickel at the temperature of 120 ℃ for 12 hours, then weighing 57.00kg of niobium-chromium alloy and 43.00kg of electrolytic nickel, uniformly mixing, putting into a knotted and dried corundum crucible, vacuumizing a medium-frequency vacuum induction smelting furnace to below 10Pa to remove gas in the furnace, setting the initial power to be 20kW, adjusting the power to be 30kW after 10min, and adjusting the power to be 80kW after 20min until the alloy is completely melted; finally, adjusting the power to 100kW, refining for 5min under the conditions of 100kW power and 1900 ℃, vacuumizing the medium-frequency vacuum induction smelting furnace to below 10Pa again, and removing oxygen elements in the melt to obtain nickel-niobium-chromium alloy liquid;
(3) adjusting the power of the medium-frequency vacuum induction melting furnace to 80kW, inclining the crucible, slowly and stably pouring the nickel-niobium-chromium alloy liquid into a water-cooled crucible, and keeping vacuum cooling for 12h to obtain the nickel-niobium-chromium intermediate alloy.
Example 2
The preparation method of the nickel-niobium-chromium intermediate alloy specifically comprises the following steps:
(1) respectively drying niobium pentoxide, chromium trioxide and aluminum powder at the temperature of 119 ℃ for 12 hours, then weighing 92.83kg of niobium pentoxide, 51.29kg of chromium trioxide and 49.63kg of aluminum powder, putting the weighed materials into a V-shaped mixer, fully mixing the materials uniformly, putting the uniformly mixed furnace burden into a sintered corundum crucible for ignition reaction at the thermit reaction temperature of 1920 ℃ for 45 seconds, cooling the mixture for 12 hours, removing the crucible, taking out an alloy ingot, removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing the alloy ingot to 5-50mm, and carrying out magnetic separation and manual selection to obtain the niobium-chromium alloy;
(2) firstly, respectively drying niobium-chromium alloy and electrolytic nickel at the temperature of 120 ℃ for 12 hours, then weighing 57.00kg of niobium-chromium alloy and 43.00kg of electrolytic nickel, uniformly mixing, putting into a knotted and dried corundum crucible, vacuumizing a medium-frequency vacuum induction smelting furnace to below 10Pa to remove gas in the furnace, setting the initial power to be 20kW, adjusting the power to be 30kW after 10min, and adjusting the power to be 80kW after 20min until the alloy is completely melted; finally, adjusting the power to 100kW, refining for 6min under the conditions of 100kW power and 1880 ℃, vacuumizing the medium-frequency vacuum induction melting furnace to below 10Pa again, and removing oxygen elements in the melt to obtain nickel-niobium-chromium alloy liquid;
(3) adjusting the power of the medium-frequency vacuum induction melting furnace to 80kW, inclining the crucible, slowly and stably pouring the nickel-niobium-chromium alloy liquid into a water-cooled crucible, and keeping vacuum cooling for 12h to obtain the nickel-niobium-chromium intermediate alloy.
Example 3
The preparation method of the nickel-niobium-chromium intermediate alloy specifically comprises the following steps:
(1) firstly, respectively drying niobium pentoxide, chromium trioxide and aluminum powder at the temperature of 120 ℃ for 12 hours, then weighing 96.59kg of niobium pentoxide, 47.44kg of chromium trioxide and 49.54kg of aluminum powder, putting the weighed materials into a V-shaped mixer, fully mixing the materials uniformly, putting the uniformly mixed furnace burden into a sintered corundum crucible for ignition reaction at the temperature of 1900 ℃ for 46 seconds, cooling the mixture for 12 hours, removing the crucible, taking out an alloy ingot, removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing the alloy ingot to 5-50mm, and magnetically separating and manually selecting the alloy to obtain the niobium-chromium alloy;
(2) firstly, respectively drying niobium-chromium alloy and electrolytic nickel at the temperature of 120 ℃ for 12 hours, then weighing 57.00kg of niobium-chromium alloy and 43.00kg of electrolytic nickel, uniformly mixing, putting into a knotted and dried corundum crucible, vacuumizing a medium-frequency vacuum induction smelting furnace to below 10Pa to remove gas in the furnace, setting the initial power to be 20kW, adjusting the power to be 30kW after 10min, and adjusting the power to be 80kW after 20min until the alloy is completely melted; finally, adjusting the power to 100kW, refining for 7.5min under the conditions of 100kW power and 1870 ℃, vacuumizing the medium-frequency vacuum induction melting furnace to below 10Pa again, and removing oxygen elements in the melt to obtain nickel-niobium-chromium alloy liquid;
(3) adjusting the power of the medium-frequency vacuum induction melting furnace to 80kW, inclining the crucible, slowly and stably pouring the nickel-niobium-chromium alloy liquid into a water-cooled crucible, and keeping vacuum cooling for 12h to obtain the nickel-niobium-chromium intermediate alloy.
Example 4
(1) Firstly, respectively drying niobium pentoxide, chromium trioxide and aluminum powder at the temperature of 121 ℃ for 12 hours, then weighing 100.37kg of niobium pentoxide, 41.03kg of chromium trioxide and 49.44kg of aluminum powder, putting the materials into a V-shaped mixer, fully mixing the materials uniformly, putting the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction at the temperature of 1880 ℃ for 48 seconds, cooling the mixture for 12 hours, removing the crucible, taking out an alloy ingot, removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing the alloy ingot to 5-50mm, and carrying out magnetic separation and manual selection to obtain the niobium-chromium alloy;
(2) firstly, respectively drying niobium-chromium alloy and electrolytic nickel at the temperature of 120 ℃ for 12 hours, then weighing 57.00kg of niobium-chromium alloy and 43.00kg of electrolytic nickel, uniformly mixing, putting into a knotted and dried corundum crucible, vacuumizing a medium-frequency vacuum induction smelting furnace to below 10Pa to remove gas in the furnace, setting the initial power to be 20kW, adjusting the power to be 30kW after 10min, and adjusting the power to be 80kW after 20min until the alloy is completely melted; finally, adjusting the power to 100kW, refining for 9min under the conditions of the power of 100kW and the temperature of 1860 ℃, vacuumizing the medium-frequency vacuum induction melting furnace to below 10Pa again, and removing oxygen elements in the melt to obtain nickel-niobium-chromium alloy liquid;
(3) adjusting the power of the medium-frequency vacuum induction melting furnace to 80kW, inclining the crucible, slowly and stably pouring the nickel-niobium-chromium alloy liquid into a water-cooled crucible, and keeping vacuum cooling for 12h to obtain the nickel-niobium-chromium intermediate alloy.
Example 5
(1) Firstly, respectively drying niobium pentoxide, chromium trioxide and aluminum powder at the temperature of 122 ℃ for 12 hours, then weighing 102.87kg of niobium pentoxide, 41.03kg of chromium trioxide and 49.38kg of aluminum powder, putting the materials into a V-shaped mixer, fully mixing the materials uniformly, putting the uniformly mixed furnace burden into a sintered corundum crucible for ignition reaction at the temperature of 1850 ℃ for 50 seconds, cooling for 12 hours, removing the crucible, taking out an alloy ingot, removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing to 5-50mm, and carrying out magnetic separation and manual selection to obtain the niobium-chromium alloy;
(2) firstly, respectively drying niobium-chromium alloy and electrolytic nickel at the temperature of 120 ℃ for 12 hours, then weighing 57.00kg of niobium-chromium alloy and 43.00kg of electrolytic nickel, uniformly mixing, putting into a knotted and dried corundum crucible, vacuumizing a medium-frequency vacuum induction smelting furnace to below 10Pa to remove gas in the furnace, setting the initial power to be 20kW, adjusting the power to be 30kW after 10min, and adjusting the power to be 80kW after 20min until the alloy is completely melted; finally, adjusting the power to 100kW, refining for 10min under the conditions of 100kW power and 1850 ℃, vacuumizing the medium-frequency vacuum induction melting furnace to below 10Pa again, and removing oxygen elements in the melt to obtain nickel-niobium-chromium alloy liquid;
(3) adjusting the power of the medium-frequency vacuum induction melting furnace to 80kW, inclining the crucible, slowly and stably pouring the nickel-niobium-chromium alloy liquid into a water-cooled crucible, and keeping vacuum cooling for 12h to obtain the nickel-niobium-chromium intermediate alloy.
Performance detection
1. The nickel niobium chromium intermediate alloy ingots (cylinders) prepared in examples 1 to 5 were sampled, and chemical composition analysis was performed using two points (1, 2) from the upper surface of the ingot, two points (3, 4) from the lower surface of the ingot, and two points (5, 6) from the middle portion of the ingot, and the results are shown in tables 1 to 5.
Table 1 example 1 analysis results of chemical composition of nickel niobium chromium master alloy ingot
Table 2 example 2 analysis results of chemical composition of ni-nb-cr master alloy ingot
Table 3 example 3 analysis results of chemical composition of ni-nb-cr master alloy ingot
Table 4 example 4 analysis results of chemical composition of ni-nb-cr master alloy ingot
TABLE 5 example 5 analysis of chemical composition of Ni-Nb-Cr intermediate alloy ingot
As can be seen from tables 1-5, the nickel-niobium-chromium intermediate alloy prepared in the embodiments 1-5 of the present invention has the advantages of high purity, uniform and stable components, less segregation, and lower content of gas phase impurities, and can better meet the production requirements of high temperature alloys.
2. Samples of the Ni-Nb-Cr master alloy ingots (cylinders) prepared in examples 1-5 were taken for chemical composition analysis, and the optimum results are shown in Table 6.
TABLE 6 examples 1-5 Ni Nb Cr master alloy ingots optimum results
As can be seen from Table 6, the Ni-Nb-Cr master alloys prepared in examples 1-5 of the present invention have uniform contents and low O, N impurity contents, wherein C, Fe and Si are inevitable impurities introduced from raw materials.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The nickel-niobium-chromium intermediate alloy is characterized by comprising the following components in percentage by mass: 36.0 to 41.0 percent of niobium, 16.0 to 21.0 percent of chromium, and the balance of nickel and inevitable impurities.
2. The nickel-niobium-chromium intermediate alloy as claimed in claim 1, characterized in that it comprises, in mass%: 37.0 to 40.0 percent of niobium, 17.0 to 20.0 percent of chromium, and the balance of nickel and inevitable impurities.
3. The nickel-niobium-chromium intermediate alloy as claimed in claim 2, characterized in that it comprises, in mass%: 38.5% of niobium, 18.5% of chromium, the balance of nickel and inevitable impurities.
4. A method for preparing a nickel niobium chromium master alloy as claimed in any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) mixing a niobium source, a chromium source and aluminum, and carrying out aluminothermic reaction to obtain a niobium-chromium alloy;
(2) mixing the niobium-chromium alloy and electrolytic nickel, and carrying out vacuum induction smelting to obtain a nickel-niobium-chromium alloy solution;
(3) and cooling the nickel-niobium-chromium alloy liquid to obtain the nickel-niobium-chromium intermediate alloy.
5. The method for preparing a nickel-niobium-chromium intermediate alloy as claimed in claim 4, wherein in the step (1), the niobium source, the chromium source and the aluminum are dried respectively before the niobium source, the chromium source and the aluminum are mixed; in the step (2), before the niobium-chromium alloy and the electrolytic nickel are mixed, respectively drying the niobium-chromium alloy and the electrolytic nickel;
the drying temperature is 118-122 ℃, and the drying time is more than or equal to 12 h.
6. The method for preparing the nickel-niobium-chromium intermediate alloy as claimed in claim 4, wherein in the step (1), the niobium source is niobium pentoxide, and the chromium source is chromium trioxide;
the mass ratio of niobium pentoxide to chromium trioxide to aluminum is (1.82-2.08): (0.82-1.09): (0.99-1.01).
7. The method as claimed in claim 4, wherein the thermite reaction is performed at 1850 ℃ and 1950 ℃ for 35-45s in step (1).
8. The method for preparing the nickel-niobium-chromium intermediate alloy as claimed in claim 4, wherein in the step (2), the mass ratio of the niobium-chromium alloy to the electrolytic nickel is (1.32-1.33): (0.99-1.01).
9. The method for preparing the nickel-niobium-chromium intermediate alloy as claimed in claim 4, wherein in the step (2), the vacuum induction melting comprises melting and refining which are sequentially carried out;
the vacuum degree of the vacuum induction melting is less than or equal to 10 Pa; the power of the refining is 100kW, the temperature is 1850-1900 ℃, and the time is 5-10 min.
10. The method for preparing the nickel-niobium-chromium intermediate alloy as claimed in claim 4, wherein in the step (3), the cooling time is not less than 12 h.
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