CN113355577A - Aluminum-vanadium-niobium intermediate alloy, aluminum-vanadium-niobium-titanium intermediate alloy and preparation method thereof - Google Patents

Abstract

The invention provides an aluminum-vanadium-niobium intermediate alloy, an aluminum-vanadium-niobium-titanium intermediate alloy and a preparation method thereof, belonging to the field of metal materials. The invention provides an aluminum-vanadium-niobium intermediate alloy and an aluminum-vanadium-niobium-titanium intermediate alloy, wherein aluminum is the most main strengthening element in the titanium alloy, has obvious solid solution strengthening effect, can obviously improve the high-temperature mechanical property of the titanium alloy, and simultaneously has lower density, thereby being beneficial to improving the specific strength of the titanium alloy; the vanadium has the function of strengthening the titanium alloy, and when the vanadium is added into the titanium alloy in a certain proportion, the alloy has excellent performances such as good ductility, corrosion resistance and formability; niobium can be infinitely dissolved in beta titanium to play a role in solid solution strengthening, so that the alloy strength is improved, the thermal stability of the alloy can be effectively improved, and good plasticity is maintained. The invention controls the components and the content to ensure that the components of the aluminum-vanadium-niobium and aluminum-vanadium-niobium-titanium intermediate alloy are uniform and have small segregation, and is beneficial to the homogenization of the components of the titanium alloy and the prevention of component segregation when the titanium alloy is smelted.

Description

Aluminum-vanadium-niobium intermediate alloy, aluminum-vanadium-niobium-titanium intermediate alloy and preparation method thereof

Technical Field

The invention relates to the technical field of metal materials, in particular to an aluminum-vanadium-niobium intermediate alloy, an aluminum-vanadium-niobium-titanium intermediate alloy and a preparation method thereof.

Background

Titanium and its alloy have excellent performance, such as corrosion resistance, high temperature resistance, low temperature resistance, high strength, non-magnetism, etc., have good comprehensive properties of the process at the same time, become irreplaceable materials gradually in the scientific and technical field of modern industry, have extensive application in the fields of aerospace industry, ship manufacturing industry, chemical industry, electric power industry, metallurgical industry, textile industry, food industry, medical industry, vehicle manufacturing industry, sports and leisure industry, etc.

With the continuous development of the titanium alloy industry, more and more metals are added into the titanium alloy in the form of intermediate alloy, the trouble of respectively adding metal simple substances is avoided, the melting point of the intermediate alloy is lower than the highest melting point of the metal simple substances in the intermediate alloy, the titanium alloy can be ensured to be more stable in the smelting process, and the situation that the smelting process is not easy to control due to the fact that the melting points of the added metal simple substances are inconsistent is better avoided.

Aluminum, vanadium and niobium are main alloy components of titanium alloy, and are usually added into the titanium alloy in the form of intermediate alloy, at present, the titanium alloy intermediate alloy is mostly binary alloy, and in order to meet the performance requirements in use, a plurality of binary alloys need to be added, so that the product performance is easy to be unstable, and the difficulty is brought to the intermediate process of producing the titanium alloy.

The aluminum is the most main strengthening element in the titanium alloy, has obvious solid solution strengthening effect, can obviously improve the high-temperature mechanical property of the titanium alloy, is the main alloy element which is firstly used for developing the heat-strength titanium alloy, and simultaneously has lower density, thereby being beneficial to improving the specific strength of the titanium alloy; the vanadium has the function of strengthening the titanium alloy, and when the vanadium is added into the titanium alloy in a certain proportion, the alloy has excellent performances such as good ductility, corrosion resistance and formability; niobium can be infinitely dissolved in beta titanium to play a role in solid solution strengthening, so that the alloy strength is improved, the thermal stability of the alloy can be effectively improved, and good plasticity is maintained.

When the titanium alloy is smelted, if the low-melting-point aluminum element and the high-melting-point refractory elements niobium and vanadium are added in a pure metal form, great quality hidden danger exists, segregation and inclusion metallurgical defects of a titanium alloy ingot are easily caused, and therefore the low-melting-point aluminum element and the high-melting-point refractory elements niobium and vanadium are usually added in an intermediate alloy form.

In order to meet the requirements of element content in the alloy and performance requirements during use, a plurality of binary alloys need to be added, so that the alloy proportion in the production process of the titanium alloy becomes complicated, and metallurgical defects such as segregation, inclusion and the like of a titanium alloy ingot are easily caused, and the existence of the defects can seriously affect the structure, mechanical property and subsequent use reliability of a product.

Disclosure of Invention

In view of the above, the present invention provides an aluminum vanadium niobium intermediate alloy, an aluminum vanadium niobium titanium intermediate alloy and a preparation method thereof. The Al-V-Nb intermediate alloy and the Al-V-Nb-Ti intermediate alloy provided by the invention have uniform and stable components, and are beneficial to the homogenization of alloy components when smelting a titanium alloy.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides an aluminum-vanadium-niobium intermediate alloy which comprises, by mass, 70.0-75.0% of V, 10.0-15.0% of Nb and the balance of Al.

Preferably, the alloy comprises 71.0-74.0% of V, 11.0-14.0% of Nb and the balance of Al.

Preferably, 73.0% V, 13.0% Nb and the balance Al.

The invention also provides a preparation method of the aluminum-vanadium-niobium intermediate alloy, which comprises the following steps:

mixing vanadium pentoxide, niobium pentoxide and aluminum, carrying out aluminothermic reaction, and cooling to obtain an aluminum-vanadium-niobium primary alloy;

and carrying out vacuum induction melting on the aluminum-vanadium-niobium primary alloy and aluminum, and cooling to obtain the aluminum-vanadium-niobium intermediate alloy.

Preferably, the mass ratio of the vanadium pentoxide to the niobium pentoxide to the aluminum is (1.561-1.673): (0.179-0.268): (0.980 to 1.020).

The invention provides an aluminum-vanadium-niobium-titanium intermediate alloy which comprises 67.0-71.0% of V, 11.0-15.0% of Nb, 3.0-7.0% of Ti and the balance of Al by mass.

Preferably, the alloy comprises 68.0-70.0% of V, 12.0-14.0% of Nb, 4.0-6.0% of Ti and the balance of Al.

Preferably, 69.0% V, 13.0% Nb, 5.0% Ti and the balance Al.

The invention also provides a preparation method of the aluminum-vanadium-niobium-titanium intermediate alloy in the technical scheme, which comprises the following steps:

mixing vanadium pentoxide, niobium pentoxide and aluminum, carrying out aluminothermic reaction, and cooling to obtain an aluminum-vanadium-niobium primary alloy;

and carrying out vacuum induction melting on the primary aluminum-vanadium-niobium alloy and the titanium sponge, and cooling to obtain the intermediate aluminum-vanadium-niobium-titanium alloy.

Preferably, the mass ratio of the vanadium pentoxide to the niobium pentoxide to the aluminum is (12.325-13.622): (1.622-2.307): (8.269-8.602).

The invention provides an aluminum-vanadium-niobium intermediate alloy which comprises, by mass, 70.0-75.0% of V, 10.0-15.0% of Nb and the balance of Al. In the invention, aluminum is the most main strengthening element in the titanium alloy, has obvious solid solution strengthening effect, can obviously improve the high-temperature mechanical property of the titanium alloy, and simultaneously has lower density, thus being beneficial to improving the specific strength of the titanium alloy; the vanadium has the function of strengthening the titanium alloy, and when the vanadium is added into the titanium alloy in a certain proportion, the alloy has excellent performances such as good ductility, corrosion resistance and formability; niobium can be infinitely dissolved in beta titanium to play a role in solid solution strengthening, so that the alloy strength is improved, the thermal stability of the alloy can be effectively improved, and good plasticity is maintained. The invention ensures that the Al-V-Nb master alloy has uniform components and small segregation by controlling the components and the content, and is beneficial to the homogenization of the components of the titanium alloy and the prevention of component segregation when the titanium alloy is smelted.

The invention provides a preparation method of the aluminum-vanadium-niobium intermediate alloy in the technical scheme. The invention adopts a two-step method to prepare the aluminum-vanadium-niobium intermediate alloy, namely the two steps of thermite reduction reaction and vacuum induction melting: preparing an aluminum-vanadium-niobium primary alloy with the grade similar to that of a target alloy by adopting an aluminothermic method; and then carrying out vacuum induction smelting, wherein the aluminum-vanadium-niobium primary alloy is used as a matrix during the vacuum induction smelting, and the aluminum is added to adjust the grade of the primary alloy, so that the grade of the target alloy is more stable. The preparation method provided by the invention can improve the uniform stability of the components of the aluminum-vanadium-niobium intermediate alloy, reduce the impurity content and better meet the production requirements of titanium alloys.

The invention also provides an aluminum-vanadium-niobium-titanium intermediate alloy which comprises 67.0-71.0% of V, 11.0-15.0% of Nb, 3.0-7.0% of Ti and the balance of Al by mass. In the invention, aluminum is the most main strengthening element in the titanium alloy, has obvious solid solution strengthening effect, can obviously improve the high-temperature mechanical property of the titanium alloy, and simultaneously has lower density, thus being beneficial to improving the specific strength of the titanium alloy; the vanadium has the function of strengthening the titanium alloy, and when the vanadium is added into the titanium alloy in a certain proportion, the alloy has excellent performances such as good ductility, corrosion resistance and formability; niobium can be infinitely dissolved in beta titanium to play a role in solid solution strengthening, so that the alloy strength is improved, the thermal stability of the alloy can be effectively improved, and good plasticity is maintained; ti is a matrix element. The invention controls the components and the content to ensure that the Al-V-Nb-Ti intermediate alloy has uniform components and small segregation, and is beneficial to the homogenization of the components of the titanium alloy and the prevention of component segregation when the titanium alloy is smelted.

The invention also provides a preparation method of the aluminum-vanadium-niobium-titanium intermediate alloy in the technical scheme. The invention adopts a two-step method to prepare the aluminum-vanadium-niobium-titanium intermediate alloy, namely the two steps of thermite reduction reaction and vacuum induction melting: preparing an aluminum-vanadium-niobium primary alloy by adopting an aluminothermic method; and then carrying out vacuum induction melting, wherein the aluminum-niobium-vanadium-titanium intermediate alloy is prepared by taking the aluminum-vanadium-niobium primary alloy and the sponge titanium as raw materials during the vacuum induction melting. The preparation method provided by the invention can improve the uniform stability of the components of the aluminum-vanadium-niobium-titanium intermediate alloy, reduce the impurity content and better meet the production requirements of titanium alloys.

Detailed Description

The invention provides an aluminum-vanadium-niobium intermediate alloy which comprises, by mass, 70.0-75.0% of V, 10.0-15.0% of Nb and the balance of Al, preferably 71.0-74.0% of V, 11.0-14.0% of Nb and the balance of Al, and more preferably 73.0% of V, 13.0% of Nb and the balance of Al.

The invention controls the components and the content to ensure that the Al-V-Nb master alloy has uniform components and small segregation, and is beneficial to the homogenization of the components of the titanium alloy and the prevention of component segregation when the titanium alloy is smelted.

The invention provides a preparation method of the aluminum-vanadium-niobium intermediate alloy, which comprises the following steps:

mixing vanadium pentoxide, niobium pentoxide and aluminum, carrying out aluminothermic reaction, and cooling to obtain an aluminum-vanadium-niobium primary alloy;

and carrying out vacuum induction melting on the aluminum-vanadium-niobium primary alloy and aluminum, and cooling to obtain the aluminum-vanadium-niobium intermediate alloy.

According to the invention, vanadium pentoxide, niobium pentoxide and aluminum are mixed for aluminothermic reaction, and the aluminum vanadium niobium primary alloy is obtained after cooling.

In the invention, the mass ratio of the vanadium pentoxide to the niobium pentoxide to the aluminum is preferably (1.561-1.673): (0.179-0.268): (0.980 to 1.020), more preferably (1.584 to 1.651): (0.197-0.250): (0.988 to 1.012), most preferably 1.628: 0.232: 0.996.

in the invention, the vanadium pentoxide, the niobium pentoxide and the aluminum are preferably powder; the vanadium pentoxide, the niobium pentoxide and the aluminum are preferably dried before being mixed, the drying temperature is preferably 110-130 ℃, more preferably 120 ℃, and the drying time is preferably not less than 6 hours, more preferably 12 hours. In the invention, the drying can remove water in the vanadium pentoxide, the niobium pentoxide and the aluminum, and prevent the hydrogen evolution phenomenon in the smelting process.

The method has no special requirement on the mixing method, and the method well known in the field is adopted to ensure that the vanadium pentoxide, the niobium pentoxide and the aluminum are uniformly mixed; in the specific embodiment of the invention, the mixing is preferably performed in a V-shaped mixer, the mixing speed of the mixer is preferably 100-140 r/min, more preferably 110-130 r/min, and the mixing time is preferably 2-6 min, more preferably 3-5 min. In the invention, the mixing makes the components fully contacted, so that the thermite reaction is conveniently carried out.

According to the invention, the mixture obtained by mixing is preferably placed in a reaction crucible for aluminothermic reaction. In the present invention, the reaction crucible is preferably prepared from graphite, magnesia brick or corundum, and more preferably from corundum, so that the introduction of other elements is avoided and the reaction crucible can be recycled.

The present invention does not require any particular ignition means for initiating the thermite reaction and may be accomplished in a manner well known in the art.

In the invention, the temperature of the thermite reaction is preferably 1700-1800 ℃, more preferably 1730-1770 ℃, and the time is preferably 35-45 s, more preferably 38-42 s.

The invention has no special requirement on the reaction device of the aluminothermic reaction, and only needs to adopt the aluminothermic reaction device well known in the field, in the specific embodiment of the invention, the aluminothermic reaction is preferably carried out in a smelting furnace, and the furnace body of the smelting furnace is preferably a furnace body built by magnesia bricks, a furnace body sintered by aluminum oxide or a furnace body built by graphite plates.

In the invention, in the aluminothermic reaction process, aluminum is used as a reducing agent to reduce vanadium pentoxide and niobium pentoxide into metal simple substances vanadium and niobium respectively, aluminum is oxidized into aluminum oxide, a large amount of heat energy is released to melt metals (the metal simple substances vanadium, niobium and excessive aluminum) to form aluminum-vanadium-niobium alloy liquid, and aluminum oxide formed by oxidizing aluminum floats on the surface of the alloy liquid and is separated from the alloy liquid and removed.

After the aluminum vanadium niobium alloy liquid is obtained, the aluminum vanadium niobium alloy liquid is cooled. In the present invention, the cooling is preferably furnace cooling, and the cooling time is preferably 12 hours.

After cooling, the invention also preferably carries out finishing crushing, component analysis and selection on the cooled alloy ingot in sequence. The method of the present invention for the size reduction and the composition analysis is not particularly required, and the corresponding method well known in the art may be employed. In the invention, the selection preferably comprises magnetic separation and manual selection; the invention selects the magnetic impurities, the alloy containing the oxide film and the nitride film, and selects the qualified part as the primary alloy of the aluminum, vanadium and niobium. The invention takes aluminum as a reducing agent, vanadium pentoxide and niobium pentoxide as oxidizing agents, and prepares the aluminum vanadium niobium primary alloy with the grade similar to that of the target alloy through aluminothermic reaction (namely an external ignition method).

After the aluminum vanadium niobium primary alloy is obtained, the aluminum vanadium niobium primary alloy and aluminum are subjected to vacuum induction melting and cooling to obtain the aluminum vanadium niobium intermediate alloy.

In the invention, the adding amount of the aluminum-vanadium-niobium primary alloy and aluminum in the vacuum melting is preferably determined according to the component analysis result of the aluminum-vanadium-niobium primary alloy and the mass content of each metal element in the needed aluminum-vanadium-niobium intermediate alloy; in a particular embodiment of the invention, the aluminum is preferably added in the form of aluminum beans.

In the invention, 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, the aluminum-vanadium-niobium primary alloy and aluminum are placed in the corundum crucible, and then the corundum crucible is placed in the medium-frequency vacuum induction furnace for melting.

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 percent; the furnace lining for knotting the corundum crucible is preferably prepared by adopting the aluminothermic reaction slag (alumina), so that reaction raw materials are fully utilized, the cost is saved, and the method for preparing the furnace lining for knotting the corundum crucible has no special requirement and can be realized by adopting a method well known in the field.

In the invention, the vacuum degree is preferably less than 10 Pa when the vacuum induction melting is vacuumized; the vacuum induction melting is preferably carried out in a protective atmosphere, preferably argon.

In the present invention, the vacuum induction melting preferably includes melting and refining which are sequentially performed. In the present invention, the melting is particularly preferably: and adjusting the power of the medium-frequency vacuum induction furnace to the initial power to start heating, then increasing the power to the transition power to heat until the metal starts to melt, and then increasing the power to the stable power to heat until the metal is completely melted to obtain a mixed melt. In the invention, the initial power is preferably 35-40 kW, and more preferably 38-40 kW; the transition power is preferably 45-60 kW, and more preferably 50-60 kW; the stable power is preferably 62-70 kW, and more preferably 68-70 kW.

After the primary alloy of aluminum, vanadium and niobium and aluminum are completely melted, the mixed melt is refined. In the invention, the refining temperature is preferably 1750-1850 ℃, more preferably 1780-1820 ℃, and the time is preferably 5-10 min, more preferably 6-8 min. In the refining process, the power of the medium-frequency vacuum induction furnace is preferably 75-80 kW, more preferably 80kW, and in the refining process, impurities and gases in the mixed melt can be removed to obtain pure alloy liquid.

After the refining is finished, the obtained alloy liquid is cooled. The alloy liquid obtained by induction melting is preferably cast in a water-cooled copper crucible for cooling, the preferable time of cooling is more than or equal to 6h, the invention has no special requirement on the casting operation and only needs to adopt a casting method well known in the field, and the invention has no special requirement on the water-cooled copper crucible and only needs to adopt a water-cooled copper crucible well known in the field.

In the present invention, the cooling is preferably performed under vacuum conditions.

According to the invention, during vacuum induction smelting, the primary aluminum-vanadium-niobium alloy is used as a matrix, and aluminum is added to adjust the grade of the primary alloy, so that the grade of the target alloy is more stable, and meanwhile, a good smelting environment is provided for the primary aluminum-vanadium-niobium alloy; and the content of gaseous impurities in the target alloy can be reduced.

The preparation method provided by the invention can improve the uniform stability and accuracy of the components of the aluminum-vanadium-niobium intermediate alloy, reduce the impurity content and better meet the production requirements of titanium alloy.

The invention also provides an aluminum-vanadium-niobium-titanium intermediate alloy which comprises 67.0-71.0% of V, 11.0-15.0% of Nb, 3.0-7.0% of Ti and the balance of Al by mass, preferably 68.0-70.0% of V, 12.0-14.0% of Nb, 4.0-6.0% of Ti and the balance of Al, more preferably 69.0% of V, 13.0% of Nb, 5.0% of Ti and the balance of Al.

The invention controls the components and the content to ensure that the Al-V-Nb-Ti intermediate alloy has uniform components and small segregation, and is beneficial to the homogenization of the components of the titanium alloy and the prevention of component segregation when the titanium alloy is smelted.

The invention also provides a preparation method of the aluminum-vanadium-niobium-titanium intermediate alloy in the technical scheme, which comprises the following steps:

mixing vanadium pentoxide, niobium pentoxide and aluminum, carrying out aluminothermic reaction, and cooling to obtain an aluminum-vanadium-niobium primary alloy;

and carrying out vacuum induction melting on the primary aluminum-vanadium-niobium alloy and the titanium sponge, and cooling to obtain the intermediate aluminum-vanadium-niobium-titanium alloy.

According to the invention, vanadium pentoxide, niobium pentoxide and aluminum are mixed for aluminothermic reaction, and the mixture is cooled to obtain the primary aluminum-vanadium-niobium alloy.

In the invention, the mass ratio of vanadium pentoxide to niobium pentoxide to aluminum is preferably (12.325-13.622): (1.622-2.307): (8.269-8.602), more preferably (12.639-13.287): (1.788-2.130): (8.355-8.522), most preferably 12.960: 1.957: 8.439.

in the invention, the vanadium pentoxide, the niobium pentoxide and the aluminum are preferably powder; the vanadium pentoxide, the niobium pentoxide and the aluminum are preferably dried before being mixed, the drying temperature is preferably 110-130 ℃, more preferably 120 ℃, and the drying time is preferably not less than 6 hours, more preferably 12 hours. In the invention, the drying can remove water in the vanadium pentoxide, the niobium pentoxide and the aluminum, and prevent the hydrogen evolution phenomenon in the smelting process.

The method has no special requirement on the mixing method, and the method well known in the field is adopted to ensure that the vanadium pentoxide, the niobium pentoxide and the aluminum are uniformly mixed; in a particular embodiment of the invention, the mixing is preferably carried out in a V-blender. The material mixing speed of the material mixer is preferably 100-140 r/min, more preferably 110-130 r/min, and the material mixing time is preferably 2-6 min, more preferably 3-5 min. In the invention, the mixing makes the components fully contacted, so that the thermite reaction is conveniently carried out.

According to the invention, the mixture obtained by mixing is preferably placed in a reaction crucible for aluminothermic reaction.

In the present invention, the aluminothermic reaction crucible is preferably prepared from graphite, magnesia brick or corundum, and more preferably from corundum, so as to avoid the introduction of other elements and to be recycled.

The present invention does not require any particular ignition means for initiating the thermite reaction and may be accomplished in a manner well known in the art.

In the invention, the thermite reaction temperature is preferably 1650-1750 ℃, more preferably 1680-1720 ℃, and the time is preferably 32-42 s, more preferably 35-39 s.

The invention has no special requirement on the reaction device of the aluminothermic reaction, and only needs to adopt the aluminothermic reaction device well known in the field, in the specific embodiment of the invention, the aluminothermic reaction is preferably carried out in a smelting furnace, and the furnace body of the smelting furnace is preferably a furnace body built by magnesia bricks, a furnace body sintered by aluminum oxide or a furnace body built by graphite plates.

In the invention, in the aluminothermic reaction process, aluminum is used as a reducing agent to reduce vanadium pentoxide and niobium pentoxide into metal simple substances vanadium and niobium respectively, aluminum is oxidized into aluminum oxide, a large amount of heat energy is released to melt metals (the metal simple substances vanadium, niobium and excessive aluminum) to form aluminum-vanadium-niobium alloy liquid, and aluminum oxide formed by oxidizing aluminum floats on the surface of the alloy liquid and is separated from the alloy liquid and removed.

After the aluminothermic reaction is carried out to obtain the aluminum vanadium niobium alloy liquid, the aluminum vanadium niobium alloy liquid is cooled. In the present invention, the cooling is preferably furnace cooling, and the cooling time is preferably 12 hours.

After cooling, the invention also preferably carries out finishing crushing, component analysis and selection on the cooled alloy ingot in sequence. The method of the present invention for the size reduction and the composition analysis is not particularly required, and the corresponding method well known in the art may be employed. In the invention, the selection preferably comprises magnetic separation and manual selection; the invention selects out magnetic impurities, oxide-containing film, nitride film alloy and other impurities, and selects qualified parts as the primary alloy of Al-V-Nb. The invention takes aluminum as a reducing agent and vanadium pentoxide and niobium pentoxide as oxidizing agents, and prepares the primary aluminum-vanadium-niobium alloy through aluminothermic reaction (namely an external ignition method).

After the primary aluminum vanadium niobium alloy is obtained, the primary aluminum vanadium niobium alloy and titanium sponge are subjected to vacuum induction melting, and the intermediate aluminum vanadium niobium titanium alloy is obtained after cooling.

In the invention, the adding amount of the aluminum-vanadium-niobium primary alloy and the titanium sponge in the vacuum melting is determined according to the analysis result of the components of the aluminum-vanadium-niobium primary alloy and the mass content of each metal element in the needed aluminum-vanadium-niobium-titanium intermediate alloy.

In the invention, 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, the aluminum-vanadium-niobium primary alloy and the titanium sponge are placed in the corundum crucible, and then the corundum crucible is placed in the medium-frequency vacuum induction furnace for melting.

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 percent; the furnace lining for knotting the corundum crucible is preferably prepared by adopting the aluminothermic reaction slag (alumina), so that reaction raw materials are fully utilized, the cost is saved, and the method for preparing the furnace lining for knotting the corundum crucible has no special requirement and can be realized by adopting a method well known in the field.

In the invention, the vacuum degree is preferably less than 10 Pa when the vacuum induction melting is vacuumized; the vacuum induction melting is preferably carried out in a protective atmosphere, preferably argon.

In the present invention, the vacuum induction melting preferably includes melting and refining which are sequentially performed. In the present invention, the melting is particularly preferably: and adjusting the power of the medium-frequency vacuum induction furnace to the initial power to start heating, then increasing the power to the transition power to heat until the metal starts to melt, and then increasing the power to the stable power to heat until the metal is completely melted to obtain a mixed melt. In the invention, the initial power is preferably 35-42 kW, and more preferably 38-40 kW; the transition power is preferably 45-65 kW, and more preferably 50-60 kW; the stable power is preferably 65-75 kW, more preferably 68-72 kW, and after the primary aluminum-vanadium-niobium alloy and the titanium sponge are completely melted, the mixed melt is refined.

In the invention, the refining temperature is preferably 1750-1850 ℃, more preferably 1780-1820 ℃, and the time is preferably 5-10 min, more preferably 6-8 min.

In the refining process, the power of the medium-frequency vacuum induction furnace is preferably 75-85 kW, and more preferably 80 kW. In the invention, the refining can remove impurities and gases in the mixed melt to obtain pure alloy liquid.

After the refining is finished, the obtained alloy liquid is cooled. According to the invention, the alloy liquid obtained by vacuum induction melting is preferably cast in a water-cooled copper crucible for cooling, and the cooling time is preferably more than or equal to 6 h. The invention has no special requirements on the casting operation and can adopt a casting method well known in the field, and the invention has no special requirements on the water-cooled copper crucible and can adopt a water-cooled copper crucible well known in the field. The cooling is preferably carried out under vacuum. And cooling to obtain the aluminum vanadium niobium titanium intermediate alloy.

The invention takes the primary alloy of aluminum, vanadium and niobium and the titanium sponge as raw materials during vacuum induction melting, so that the grade of the target alloy is more stable, and the content of gas impurities in the target alloy can be reduced.

The invention provides the preparation method of the aluminum-vanadium-niobium-titanium primary alloy, which can improve the uniform stability and accuracy of the components of the aluminum-vanadium-niobium-titanium intermediate alloy, reduce the impurity content and better meet the production requirement of the titanium alloy.

In order to further illustrate the present invention, the aluminum vanadium niobium master alloy, the aluminum vanadium niobium titanium master alloy and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 87.60kg of aluminum powder, 14.30kg of niobium pentoxide and 124.90kg of vanadium pentoxide; the raw materials are put into a V-shaped mixer, the mixing speed is 140r/min, the mixing time is 2min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain an aluminum-vanadium-niobium primary alloy, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 95.00kg of aluminum-vanadium-niobium primary alloy and 5.00kg of aluminum beans; and (3) putting the primary alloy and the aluminum beans into a knotted and dried corundum crucible. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after the furnace burden is completely melted, refining is carried out for 10 minutes at 1750 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum-vanadium-niobium intermediate alloy (cylinder).

One position of the aluminum vanadium niobium intermediate alloy prepared in this example was sampled and analyzed for chemical composition, and the results are shown in table 1. As can be seen from Table 1, the Al-V-Nb master alloy C, O, N prepared in this example has a low impurity content, wherein Fe and Si are inevitable impurities introduced from raw materials.

The Al-V-Nb master alloy prepared in this example was sampled at different positions, and subjected to chemical composition analysis, wherein two points, numbered 1 and 2, were taken from the upper surface of the alloy ingot, two points, numbered 3 and 4, were taken from the lower surface of the alloy ingot, and two points, numbered 5 and 6, were taken from the middle portion of the alloy ingot, and the composition analysis was performed on the points, and the results are shown in Table 2. As can be seen from Table 2, the Al-V-Nb master alloy prepared in this example has uniform and stable components and no segregation.

Example 2

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 80.97kg of aluminum powder, 15.73kg of niobium pentoxide and 126.69kg of vanadium pentoxide; the raw materials are put into a V-shaped mixer, the mixing speed is 130r/min, the mixing time is 3min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain an aluminum-vanadium-niobium primary alloy, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 95.00kg of aluminum-vanadium-niobium primary alloy and 5.00kg of aluminum beans; and (3) putting the primary alloy and the aluminum beans into a knotted and dried corundum crucible. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after the furnace burden is completely melted, refining is carried out for 8 minutes at 1780 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum-vanadium-niobium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the aluminum vanadium niobium master alloy prepared in the example was sampled and analyzed for chemical composition, and the results are shown in table 1.

The method of example 1 is adopted to sample different parts of the aluminum vanadium niobium master alloy prepared in this example for chemical composition analysis, and the results are shown in table 3, which shows that the aluminum vanadium niobium master alloy prepared in this example has uniform and stable composition and no segregation.

Example 3

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 79.70kg of aluminum powder, 18.59kg of niobium pentoxide and 130.25kg of vanadium pentoxide; the raw materials are put into a V-shaped mixer, the mixing speed is 120r/min, the mixing time is 4min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain an aluminum-vanadium-niobium primary alloy, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 95.00kg of aluminum-vanadium-niobium primary alloy and 5.00kg of aluminum beans; and (3) putting the primary alloy and the aluminum beans into a knotted and dried corundum crucible. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, refining is carried out for 7 minutes at 1800 ℃ after furnace materials are completely melted, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum-vanadium-niobium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the aluminum vanadium niobium master alloy prepared in the example was sampled and analyzed for chemical composition, and the results are shown in table 1.

The method of example 1 is adopted to sample different parts of the aluminum vanadium niobium master alloy prepared in this example for chemical composition analysis, and the results are shown in table 4, which indicates that the aluminum vanadium niobium master alloy prepared in this example has uniform and stable composition and no segregation.

Example 4

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 79.07kg of aluminum powder, 20.02kg of niobium pentoxide and 132.04kg of vanadium pentoxide; the raw materials are loaded into a V-shaped mixer, the mixing speed is 110r/min, the mixing time is 5min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain an aluminum-vanadium-niobium primary alloy, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 95.00kg of aluminum-vanadium-niobium primary alloy and 5.00kg of aluminum beans; and (3) putting the primary alloy and the aluminum beans into a knotted and dried corundum crucible. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after furnace burden is completely melted, refining is carried out for 6 minutes at 1820 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum-vanadium-niobium intermediate alloy (cylinder).

The Al-V-Nb master alloy prepared in this example was sampled from one position (the same position as the sampling position in example 1) and analyzed for chemical composition, and the results are shown in Table 1.

The method of example 1 is used to sample different parts of the al-v-nb master alloy ingot (cylinder) prepared in this example for chemical composition analysis, and the results are shown in table 5, which indicates that the al-v-nb master alloy prepared in this example has uniform and stable composition and no segregation.

Example 5

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 78.43kg of aluminum powder, 21.45kg of niobium pentoxide and 133.82kg of vanadium pentoxide; the raw materials are loaded into a V-shaped mixer, the mixing speed is 100r/min, the mixing time is 6min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain an aluminum-vanadium-niobium primary alloy, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 95.00kg of aluminum-vanadium-niobium primary alloy and 5.00kg of aluminum beans; and (3) putting the primary alloy and the aluminum beans into a knotted and dried corundum crucible. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after the furnace burden is completely melted, refining is carried out for 5 minutes at 1850 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum-vanadium-niobium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the aluminum vanadium niobium master alloy prepared in the example was sampled and analyzed for chemical composition, and the results are shown in table 1.

The method of example 1 is adopted to sample different parts of the aluminum vanadium niobium master alloy prepared in this example for chemical composition analysis, and the results are shown in table 6, which indicates that the aluminum vanadium niobium master alloy prepared in this example has uniform and stable composition and no segregation.

TABLE 1 chemical composition of Al-V-Nb master alloy in examples 1-5

TABLE 2 EXAMPLE 1 Al-V-Nb interalloy different site chemistries

TABLE 3 EXAMPLE 2 Al-V-Nb interalloy different site chemistries

TABLE 4 EXAMPLE 3 Al-V-Nb interalloy different site chemistries

TABLE 5 EXAMPLE 4 Al-V-Nb master alloy different site chemistries

TABLE 6 EXAMPLE 5 Al-V-Nb interalloy different site chemistries

The embodiment shows that the aluminum-vanadium-niobium intermediate alloy provided by the 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 titanium alloys.

Example 6

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 86.02kg of aluminum powder, 16.22kg of niobium pentoxide and 123.25kg of vanadium pentoxide; the raw materials are put into a V-shaped mixer, the mixing speed is 140r/min, the mixing time is 2min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain the primary alloy of aluminum, vanadium and niobium, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 97.00kg of primary alloy of aluminum, vanadium and niobium and 3.00kg of sponge titanium; and (3) putting the primary alloy and the sponge titanium into a corundum crucible which is knotted and dried. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after the furnace burden is completely melted, refining is carried out for 10 minutes at 1750 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum vanadium niobium titanium intermediate alloy (cylinder).

One position of the al-v-nb-ti master alloy prepared in this example was sampled and analyzed for chemical composition, and the results are shown in table 7. As can be seen from table 7, the content of the aluminum vanadium niobium titanium master alloy C, O, N impurity prepared in this example is low, wherein Fe and Si are inevitable impurities introduced by the raw materials.

The Al-V-Nb-Ti intermediate alloy prepared in this example was sampled at different positions, and subjected to chemical composition analysis, wherein two points, numbered 1 and 2, were taken from the upper surface of the alloy ingot, two points, numbered 3 and 4, were taken from the lower surface of the alloy ingot, two points, numbered 5 and 6, were taken from the middle portion of the alloy ingot, and the results obtained by analyzing the components of the points were shown in Table 8. As can be seen from Table 8, the Al-V-Nb-Ti master alloy prepared in this example has uniform and stable components and no segregation.

Example 7

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 85.22kg of aluminum powder, 17.88kg of niobium pentoxide and 126.39kg of vanadium pentoxide; the raw materials are put into a V-shaped mixer, the mixing speed is 130r/min, the mixing time is 3min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain the primary alloy of aluminum, vanadium and niobium, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 96.00kg of Al-V-Nb primary alloy and 4.00kg of sponge titanium; and (3) putting the primary alloy and the sponge titanium into a corundum crucible which is knotted and dried. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after the furnace burden is completely melted, refining is carried out for 8 minutes at 1780 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum vanadium niobium titanium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the Al-V-Nb-Ti intermediate alloy prepared in this example was sampled and analyzed for chemical composition, and the results are shown in Table 7.

The method of example 1 is adopted to sample different parts of the aluminum vanadium niobium titanium intermediate alloy prepared in this example for chemical composition analysis, and the results are shown in table 9, which indicates that the aluminum vanadium niobium titanium intermediate alloy prepared in this example has uniform and stable composition and no segregation.

Example 8

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 84.39kg of aluminum powder, 19.57kg of niobium pentoxide and 129.60kg of vanadium pentoxide; the raw materials are put into a V-shaped mixer, the mixing speed is 120r/min, the mixing time is 4min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain the primary alloy of aluminum, vanadium and niobium, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 95.00kg of primary alloy of aluminum, vanadium and niobium and 5.00kg of sponge titanium; and (3) putting the primary alloy and the sponge titanium into a corundum crucible which is knotted and dried. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, refining is carried out for 7 minutes at 1800 ℃ after furnace materials are completely melted, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum vanadium niobium titanium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the Al-V-Nb-Ti intermediate alloy prepared in this example was sampled and analyzed for chemical composition, and the results are shown in Table 7.

The method of example 1 is used to sample different parts of the al-v-nb-ti master alloy ingot (cylinder) prepared in this example for chemical composition analysis, and the results are shown in table 10, which indicates that the al-v-nb-ti master alloy prepared in this example has uniform and stable composition and no segregation.

Example 9

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 79.07kg of aluminum powder, 20.02kg of niobium pentoxide and 132.04kg of vanadium pentoxide; the raw materials are loaded into a V-shaped mixer, the mixing speed is 110r/min, the mixing time is 5min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain the primary alloy of aluminum, vanadium and niobium, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 94.00kg of primary alloy of aluminum, vanadium and niobium and 6.00kg of sponge titanium; and (3) putting the primary alloy and the sponge titanium into a corundum crucible which is knotted and dried. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after furnace burden is completely melted, refining is carried out for 6 minutes at 1820 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum vanadium niobium titanium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the Al-V-Nb-Ti intermediate alloy prepared in this example was sampled and analyzed for chemical composition, and the results are shown in Table 7.

The method of example 1 is adopted to sample different parts of the aluminum vanadium niobium titanium intermediate alloy prepared in this example for chemical composition analysis, and the results are shown in table 11, which indicates that the aluminum vanadium niobium titanium intermediate alloy prepared in this example has uniform and stable composition and no segregation.

Example 10

First, aluminothermic smelting process

(1) And drying the aluminum powder, the niobium pentoxide and the vanadium pentoxide at the drying temperature of 120 ℃ for 12 hours.

(2) The raw material ratio is as follows: 78.43kg of aluminum powder, 21.45kg of niobium pentoxide and 133.82kg of vanadium pentoxide; the raw materials are loaded into a V-shaped mixer, the mixing speed is 100r/min, the mixing time is 6min, and the raw materials are uniformly mixed and fully contacted.

(3) And (3) loading the uniformly mixed furnace burden into a sintered corundum crucible, carrying out ignition reaction, cooling for 12 hours along with the furnace after the reaction is finished, dismantling the crucible, taking out an alloy ingot, and weighing.

(4) Removing a slag layer and an oxide film on the surface of the alloy ingot, crushing and finishing, carrying out magnetic separation and manual selection to obtain the primary alloy of aluminum, vanadium and niobium, and carrying out chemical component analysis on the obtained primary alloy.

Second, induction melting process

(1) The raw material ratio is as follows: 93.00kg of primary alloy of aluminum, vanadium and niobium and 7.00kg of sponge titanium; and (3) putting the primary alloy and the sponge titanium into a corundum crucible which is knotted and dried. And vacuumizing the intermediate-frequency vacuum induction smelting furnace to below 10 Pa, and removing gas impurities in the smelting furnace.

(2) And (3) power transmission smelting, wherein the initial power is 40kW, the transition power is adjusted to 60kW within 30 minutes, the stable power is adjusted to 70kW after the alloy starts to melt, after the furnace burden is completely melted, refining is carried out for 5 minutes at 1850 ℃, the smelting furnace is vacuumized to below 10 Pa again, and gas impurities in the melt are removed.

(3) The crucible is inclined, and the melt is slowly and stably cast into the water-cooled crucible. And after the casting is finished, keeping vacuum cooling for more than 6 hours to obtain the aluminum vanadium niobium titanium intermediate alloy (cylinder).

One position (same as the sampling position of the example 1) of the Al-V-Nb-Ti intermediate alloy prepared in this example was sampled and analyzed for chemical composition, and the results are shown in Table 7.

The method of example 1 is adopted to sample different parts of the aluminum vanadium niobium titanium intermediate alloy prepared in this example for chemical composition analysis, and the results are shown in table 12, which indicates that the aluminum vanadium niobium titanium intermediate alloy prepared in this example has uniform and stable composition and no segregation.

TABLE 7 chemical compositions of Al-V-Nb-Ti intermediate alloys in examples 6 to 10

TABLE 8 EXAMPLE 6 Al-V-Nb-Ti master alloy with different site chemistries

TABLE 9 EXAMPLE 7 Al-V-Nb-Ti master alloy with different site chemistries

TABLE 10 EXAMPLE 8 Al-V-Nb-Ti master alloy with different site chemistries

TABLE 11 EXAMPLE 9 Al-V-Nb-Ti master alloy for different site chemistries

TABLE 12 EXAMPLE 10 Al V Nb Ti master alloy with different site chemistries

The embodiments show that the Al-V-Nb-Ti intermediate alloy provided by the 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 titanium alloys.

The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. The Al-V-Nb intermediate alloy is characterized by comprising 70.0-75.0% of V, 10.0-15.0% of Nb and the balance of Al by mass.

2. The Al-V-Nb master alloy according to claim 1, comprising, by mass, 71.0-74.0% V, 11.0-14.0% Nb and the balance Al.

3. The Al-V-Nb master alloy as claimed in claim 1, which comprises 73.0% V, 13.0% Nb and the balance Al by mass.

4. The method for preparing the Al-V-Nb master alloy of any one of claims 1-3, which is characterized by comprising the following steps:

mixing vanadium pentoxide, niobium pentoxide and aluminum, carrying out aluminothermic reaction, and cooling to obtain an aluminum-vanadium-niobium primary alloy;

and carrying out vacuum induction melting on the aluminum-vanadium-niobium primary alloy and aluminum, and cooling to obtain the aluminum-vanadium-niobium intermediate alloy.

5. The preparation method according to claim 4, wherein the mass ratio of the vanadium pentoxide to the niobium pentoxide to the aluminum is (1.561-1.673): (0.179-0.268): (0.980 to 1.020).

6. The Al-V-Nb-Ti intermediate alloy is characterized by comprising 67.0-71.0% of V, 11.0-15.0% of Nb, 3.0-7.0% of Ti and the balance of Al by mass.

7. The Al-V-Nb-Ti intermediate alloy as claimed in claim 6, wherein the Al-V-Nb-Ti intermediate alloy comprises 68.0-70.0% V, 12.0-14.0% Nb, 4.0-6.0% Ti and the balance Al by mass.

8. The Al-V-Nb-Ti intermediate alloy as claimed in claim 6, wherein the Al-V-Nb-Ti intermediate alloy comprises, by mass, 69.0% V, 13.0% Nb, 5.0% Ti and the balance Al.

9. The method for preparing the Al-V-Nb-Ti intermediate alloy as claimed in any one of claims 6 to 8, which is characterized by comprising the following steps:

mixing vanadium pentoxide, niobium pentoxide and aluminum, carrying out aluminothermic reaction, and cooling to obtain an aluminum-vanadium-niobium primary alloy;

and carrying out vacuum induction melting on the primary aluminum-vanadium-niobium alloy and the titanium sponge, and cooling to obtain the intermediate aluminum-vanadium-niobium-titanium alloy.

10. The preparation method according to claim 9, wherein the mass ratio of the vanadium pentoxide to the niobium pentoxide to the aluminum is (12.325-13.622): (1.622-2.307): (8.269-8.602).