Preparation method of AlV65 alloy and AlV65 alloy

Abstract

The invention discloses a preparation method of an AlV65 alloy. The preparation method comprises the following steps: mixing flake vanadium, aluminum particles, AlV65 alloy powder and a calcium-aluminum alloy, and smelting to obtain an AlV65 alloy cake; the AlV65 alloy cake is subjected to shot blasting treatment; the AlV65 alloy cake obtained after shot blasting treatment is subjected to primary crushing, and an AlV65 alloy block of the first size and AlV65 alloy powder are obtained; the AlV65 alloy block with the first size is subjected to sand blasting treatment; and carrying out secondary crushing on the AlV65 alloy block with the first size after the sand blasting treatment to obtain an AlV65 alloy block with a second size and AlV65 alloy powder.

Description

Technical Field

[0001] The invention relates to the field of alloy preparation, and in particular to a preparation method of an AlV65 alloy. Background Art

[0002] Vanadium aluminum alloy is an important additive for manufacturing titanium alloy. V and Al elements are generally added to titanium alloy in the form of intermediate alloys, which can reduce the difference in melting points between V, Al and matrix Ti and improve the uniformity of titanium alloy composition. Vanadium, as a very strong β stabilizer, can strengthen α-β titanium alloy through heat treatment, improve the high temperature stability, heat resistance and cold working properties of titanium alloy. Various vanadium-containing titanium alloys have been widely used in high temperature and corrosion resistant fields such as aerospace, aviation, and ships. Vanadium aluminum alloys are divided into different grades of products according to their grade, and the main production and sales grades are AlV55 and AlV65. The quality and application advantages of AlV65 alloy over AlV55 alloy: ⑴AlV65 alloy crystals are denser, there are no cracks in the alloy crystals, and there is basically no oxide film or nitride film that degrades the quality of titanium alloy; ⑵The initial melting temperature of AlV65 alloy is about 1670℃, which is close to the melting point of matrix sponge titanium (1668℃). Using AlV65 can accurately control the composition uniformity of smelting titanium alloy ingots. Therefore, the use of AlV65 alloy has the advantages of good compatibility with titanium alloy, high controllability of the smelting process, and uniform composition of the titanium alloy ingot.

[0003] At present, AlV65 alloy is mainly produced by aluminothermic process using graphite crucible or wet knotting smelting furnace. However, graphite crucible has the disadvantages of easily causing alloy carbon increase and difficulty in large-scale production, while wet knotting smelting furnace has the disadvantages of long furnace preparation cycle, difficulty in ensuring the stability of furnace charge reaction, and large fluctuation of alloy composition. Summary of the invention

[0004] In view of this, in order to overcome at least one aspect of the above problems, an embodiment of the present invention provides a method for preparing an AlV65 alloy, comprising the following steps: The vanadium flakes, aluminum particles, AlV65 alloy powder and calcium aluminum alloy are mixed and smelted to obtain AlV65 alloy cake; Shot blasting the AlV65 alloy cake; Crushing the AlV65 alloy cake after shot blasting to obtain AlV65 alloy blocks of a first size and the AlV65 alloy powder; performing sandblasting on the AlV65 alloy block of the first size; The AlV65 alloy block of the first size after sandblasting is crushed for the second time to obtain the AlV65 alloy block of the second size and the AlV65 alloy powder.

[0005] In some embodiments, vanadium flakes, aluminum particles, AlV65 alloy powder, and calcium aluminum alloy are mixed and smelted to obtain an alloy cake, further comprising: Mix 200-220 kg of vanadium flakes, 150-165 kg of aluminum granules, 32-38 kg of cold material, and 1.5-2.5 kg of calcium aluminum alloy.

[0006] In some embodiments, further comprising: Knot the furnace body of the smelting furnace; Place the mixture into the knotted furnace body; An ignition agent is spread over the mixture to cause the mixture to undergo a self-heating reaction.

[0007] In some embodiments, titanium powder is used as an ignition agent.

[0008] In some embodiments, the weight of the titanium powder is 100 g to 250 g.

[0009] In some embodiments, it also includes: White corundum and corundum slag are used to knot the furnace body.

[0010] In some embodiments, the AlV65 alloy cake after shot blasting is crushed once to obtain an AlV65 alloy block of a first size, further comprising: The AlV65 alloy cake is crushed to within 200mm*200mm*200mm.

[0011] In some embodiments, the AlV65 alloy block of the first size after sandblasting is subjected to secondary crushing to obtain an AlV65 alloy block of the second size, further comprising: Crushing the AlV65 alloy block of the first size into pieces of 1-6 mm; The AlV65 alloy blocks of the second size are mixed and mixed evenly, and the mixing time is ≥ 6 min.

[0012] In some embodiments, it also includes: The AlV65 alloy powder obtained from the primary crushing and the secondary crushing is recovered and further smelted.

[0013] Based on the same inventive concept, the present application also proposes an AlV65 alloy, which is prepared based on the method described in any of the above embodiments.

[0014] The present invention has one of the following beneficial technical effects: the present invention is based on Al 2 O 3-CaO slag system characteristics, determine the best slag components, so that the slag gold separation is more complete; at the same time, calcium aluminum alloy is used as a slag-making agent, which plays the dual purpose of deoxidizer and reducing agent, and the slag-making agent used can produce slag cake faster, which can block the contact between N and O in the air and the alloy, so that the O and N content is significantly reduced. It fundamentally solves the problems of difficult to ensure the reaction stability of AlV65 alloy charge and large fluctuations in alloy composition. The AlV65 alloy produced has a vanadium content of 65.4%, Si≤0.1%, Fe≤0.1%, O≤0.05%, N≤0.02%, and the product has low impurity content and stable vanadium grade. At the same time, the process is short and the operation is simple, the generated product is of good quality, high vanadium yield, and low vanadium content in corundum slag. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.

[0016] Figure 1 A schematic flow chart of a method for preparing an AlV65 alloy provided in an embodiment of the present invention; Figure 2 A structural diagram of a furnace body after knotting provided by an embodiment of the present invention; Figure 3 A structural diagram of a graphite crucible provided in an embodiment of the present invention; Figure 4 A structural diagram of another graphite crucible provided by an embodiment of the present invention; Figure 5 A flowchart of a method for preparing an AlV65 alloy provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0017] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the embodiments of the present invention are further described in detail below in combination with specific embodiments and with reference to the accompanying drawings.

[0018] It should be noted that all expressions using "first" and "second" in the embodiments of the present invention are for distinguishing two non-identical entities with the same name or non-identical parameters. It can be seen that "first" and "second" are only for the convenience of expression and should not be understood as limitations on the embodiments of the present invention. The subsequent embodiments will not explain this one by one.

[0019] According to one aspect of the present invention, an embodiment of the present invention provides a method for preparing an AlV65 alloy, such as Figure 1 As shown, it may include the steps of: The vanadium flakes, aluminum particles, AlV65 alloy powder and calcium aluminum alloy are mixed and smelted to obtain AlV65 alloy cake; Shot blasting the AlV65 alloy cake; Crushing the AlV65 alloy cake after shot blasting to obtain AlV65 alloy blocks of a first size and the AlV65 alloy powder; performing sandblasting on the AlV65 alloy block of the first size; The AlV65 alloy block of the first size after sandblasting is crushed for the second time to obtain the AlV65 alloy block of the second size and the AlV65 alloy powder.

[0020] The present invention adopts XRD to analyze the occurrence form of vanadium in slag, combined with Al 2 O 3 -CaO slag system features FactSage was used to calculate the melting points of each stage of the slag system, and the optimal slag state components were determined. Through material balance, the reaction heat was controlled at about 3400KJ, and the slag and gold were completely separated to form a pure reduction slag system. Moreover, by using calcium aluminum alloy as a slag-making agent, calcium aluminum alloy is an alloy formed by melting metallic calcium and aluminum under vacuum conditions. It is mainly used as a deoxidizer and a reducing agent for smelting high-purity metals. Its Si and Fe contents are both below 0.1%, which is less than 1 / 4 of the Si and Fe contents in lime. It has no adverse effect on the quality of vanadium aluminum alloys. While being a slag-making agent, it can also be used as a reducing agent to replace part of the aluminum powder. Because calcium aluminum alloy also acts as a reducing agent in smelting, it releases heat during smelting. Compared with the pure endothermic slag-adjusting effect of lime in smelting, adding calcium aluminum alloy can add more recycled residual alloy fine powder as cold material (the more fine powder is recycled, the more excess fine powder can be consumed, and production efficiency can be improved). Relatively speaking, the output rate of a single furnace is higher and the economy is better. In this way, according to Al 2 O 3 -CaO slag system characteristics, determine the best slag components, so that the slag gold separation is more complete; at the same time, calcium aluminum alloy is used as a slag-making agent, which plays the dual purpose of deoxidizer and reducing agent, and the slag-making agent used can produce slag cake faster, which can block the contact between N and O in the air and the alloy, so that the O and N content is significantly reduced. It fundamentally solves the problems of difficult to ensure the reaction stability of AlV65 alloy charge and large fluctuations in alloy composition. The AlV65 alloy produced has a vanadium content of 65.4%, Si≤0.1%, Fe≤0.1%, O≤0.05%, N≤0.02%, and the product has low impurity content and stable vanadium grade. At the same time, the process is short and the operation is simple, the generated product is of good quality, high vanadium yield, and low vanadium content in corundum slag.

[0021] In some embodiments, vanadium flakes, aluminum particles, AlV65 alloy powder, and calcium aluminum alloy are mixed and smelted to obtain an alloy cake, further comprising: Mix 200-220 kg of vanadium flakes, 150-165 kg of aluminum granules, 32-38 kg of cold material, and 1.5-2.5 kg of calcium aluminum alloy.

[0022] In some embodiments, further comprising: Knot the furnace body of the smelting furnace; Place the mixture into the knotted furnace body; An ignition agent is spread over the mixture to cause the mixture to undergo a self-heating reaction.

[0023] Specifically, Figure 2 As shown, when knotting the furnace body, a single-layer aluminum plate ring can be rolled as a mold with a diameter of 540-580mm; the corundum slag in the bottom plate of the smelting furnace can be planed and Figure 3 or Figure 4 The graphite crucible shown is placed in the middle of the bottom plate of the smelting furnace, and the mold is placed vertically in the middle of the graphite crucible; white corundum is filled at the bottom of the graphite crucible, and no graphite layer is visible; white corundum is filled between the mold and the inner wall of the graphite crucible (knotted working layer), with a height of 250-350mm; the furnace shell is hoisted and placed vertically on the outside of the graphite crucible, so that the distance between the furnace shell and the outer wall of the graphite crucible is kept uniform; corundum slag is filled between the furnace shell and the outer wall of the graphite crucible (knotted filling layer); the casting ring is hoisted and embedded on the top of the corundum slag layer on the inner side of the furnace shell, and the distance between the furnace shell and the outer wall of the casting ring is kept uniform. Assemble the upper ring of the furnace body, add white corundum to the upper edge of the middle ring of the dry knotted furnace body, and place it between the middle ring and the upper ring to prevent the slag from leaking from the contact gap. Add white corundum to the upper edge of the crucible cylinder, and place it between the crucible cylinder and the casting cylinder (permanent layer) to prevent the slag from leaking from the contact gap.

[0024] In some embodiments, titanium powder is used as an ignition agent.

[0025] In some embodiments, the weight of the titanium powder is 100 g to 250 g.

[0026] In some embodiments, it also includes: White corundum and corundum slag are used to knot the furnace body.

[0027] In some embodiments, the AlV65 alloy cake after shot blasting is crushed once to obtain an AlV65 alloy block of a first size, further comprising: The AlV65 alloy cake is crushed to within 200mm*200mm*200mm.

[0028] In some embodiments, the AlV65 alloy block of the first size after sandblasting is subjected to secondary crushing to obtain an AlV65 alloy block of the second size, further comprising: Crushing the AlV65 alloy block of the first size into pieces of 1-6 mm; The AlV65 alloy blocks of the second size are mixed and mixed evenly, and the mixing time is ≥ 6 min.

[0029] In some embodiments, it also includes: The AlV65 alloy powder obtained from the primary crushing and the secondary crushing is recovered and further smelted.

[0030] Specifically, Figure 5 As shown, after the furnace body is knotted, mixing of materials begins. Specifically, the vanadium flakes are first crushed to 1-3 mm, and then a predetermined amount of vanadium flakes, aluminum particles, cold material, and calcium aluminum alloy are added according to calculation, including 200-220 kg of vanadium flakes, 150-165 kg of aluminum particles, 32-38 kg of cold material, and 1.5-2.5 kg of calcium aluminum alloy. The mixing time is 4 to 8 minutes. The cold material can be the AlV65 alloy powder obtained in the production process. Since the particle size of the residual fine powder alloy cannot meet customer needs, it can be returned to the furnace not only to become an alloy that meets customer needs, but also can be used as a cold material to reduce the reaction temperature in the furnace during the production process, adjust the temperature in the furnace, and make the reaction proceed smoothly.

[0031] Then start smelting. In the middle of the charge surface, use an ignition dosage spoon to place the ignition agent, with an amount of ≤0.25 kg / furnace; light the ignition paper, put it in the furnace, ignite the ignition agent, and then ignite the charge; after the reaction is over, wait for the remaining smoke to dissipate, and lift the furnace body to the hot furnace cooling area. After the furnace body cools down for ≥8 hours, dismantle the furnace to get the alloy cake. Then the single shot blasting time is 5 to 12 minutes to remove the black oxide film; manually use a sledgehammer or hand hammer to smash the alloy block to within 200mm*200mm*200mm; place the alloy block to be sprayed flat on the sandblasting tray, and sandblast the surface oxide film; crush the alloy block to 1-6mm, mix and mix evenly, the mixing time is ≥6 min, and finally the alloy is bagged and sent out.

[0032] Example 1 Take 200kg of crushed vanadium flakes, add 150kg of aluminum particles, 32kg of cold material (AlV65 alloy fine powder), and 1.5kg of calcium aluminum alloy, put them into a mixing tank and mix for 8 minutes, put the mixed materials into the knotted furnace body, rake the materials flat, and the reaction heat is 3417KJ. Take 100g of titanium powder with a purity of 99% (particle size less than 200 mesh), spread it on the charge, transport the smelting furnace into the smelting reaction chamber, ignite the titanium powder with a burning flame, and the charge self-heating reaction proceeds rapidly. The smelting reaction is completed in about 60 seconds. After standing for about 8 hours and cooling naturally to below 150℃, disassemble the furnace body, separate the slag and alloy, and obtain 170.2kg of vanadium aluminum alloy with good crystallization, brightness, no pores, and no slag inclusions. Sampling and testing showed that the alloy contained 65.85% vanadium, 33.4% aluminum, 0.097% silicon, 0.09% iron, 0.032% oxygen and 0.01% nitrogen. The product quality met the requirements of military use, and the vanadium smelting yield was 98.5%. The vanadium content of corundum slag (cold slag) was 0.5%.

[0033] Example 2 Take 210kg of crushed vanadium flakes, add 157.2kg of aluminum particles, 35kg of cold material (AlV65 alloy fine powder), and 2kg of calcium aluminum alloy, put them into the mixing tank and mix for 8 minutes, put the mixed materials into the knotted furnace body, rake the materials flat, 3415KJ. Take 120g of titanium powder with a purity of 99% (particle size less than 200 mesh), spread it on the charge, transport the smelting furnace into the smelting reaction chamber, ignite the titanium powder with a burning flame, and the charge self-heating reaction proceeds rapidly. The smelting reaction is completed in about 60 seconds. Let it stand for about 8 hours, cool naturally to below 150℃, disassemble the furnace body, separate the slag and alloy, and obtain 178.5kg of vanadium aluminum alloy with good crystallization, brightness, no pores, and no slag inclusions. Sampling and testing showed that the alloy contained 65.80% vanadium, 33.1% aluminum, 0.085% silicon, 0.082% iron, 0.033% oxygen and 0.01% nitrogen. The product quality met the requirements of military use, and the vanadium smelting yield was 98.7%. The vanadium content of corundum slag (cold slag) was 0.45%.

[0034] Example 3 Take 220kg of crushed vanadium flakes, add 165kg of aluminum particles, 38kg of cold material (AlV65 alloy fine powder), and 2.5kg of calcium aluminum alloy, put them into the mixing tank and mix for 8 minutes, put the mixed materials into the knotted furnace body, rake the materials flat, 3415KJ. Take 250g of titanium powder with a purity of 99% (particle size less than 200 mesh), spread it on the charge, transport the smelting furnace into the smelting reaction chamber, ignite the titanium powder with a burning flame, and the charge self-heating reaction proceeds rapidly. The smelting reaction is completed in about 60 seconds. Let it stand for about 8 hours, cool naturally to below 150℃, disassemble the furnace body, separate the slag and alloy, and obtain 185.1kg of vanadium aluminum alloy with good crystallization, brightness, no pores, and no slag inclusions. Sampling and testing showed that the alloy contained 65.85% vanadium, 33.2% aluminum, 0.092% silicon, 0.089% iron, 0.03% oxygen and 0.01% nitrogen. The product quality met the requirements of military use, and the vanadium smelting yield was 98.52%. The vanadium content of corundum slag (cold slag) was 0.48%.

[0035] The smelting process used in the present invention uses flake vanadium (V2O5) as the vanadium raw material and aluminum (Al) as the reducing agent. The raw materials such as flake vanadium, aluminum particles, calcium aluminum alloy, and fine powder configured in a certain proportion are fully mixed, and the mixed materials are added into the smelting furnace, and the materials in the furnace are raked flat; a predetermined amount of titanium powder is spread flat on the upper surface of the furnace charge; the titanium powder is ignited with a burning flame to make the furnace charge in the furnace undergo an aluminothermic reaction; after the aluminothermic reaction, the furnace is cooled and the obtained alloy and slag are separated; and a vanadium aluminum alloy is obtained. In this way, according to Al 2 O 3 -CaO slag system characteristics, determine the best slag components, so that the slag gold separation is more complete; at the same time, calcium aluminum alloy is used as a slag-making agent, which plays the dual purpose of deoxidizer and reducing agent, and the slag-making agent used can produce slag cake faster, which can block the contact between N and O in the air and the alloy, so that the O and N content is significantly reduced. It fundamentally solves the problems of difficult to ensure the reaction stability of AlV65 alloy charge and large fluctuations in alloy composition. The AlV65 alloy produced has a vanadium content of 65.4%, Si≤0.1%, Fe≤0.1%, O≤0.05%, N≤0.02%, and the product has low impurity content and stable vanadium grade. At the same time, the process is short and the operation is simple, the generated product is of good quality, high vanadium yield, and low vanadium content in corundum slag.

[0036] Based on the same inventive concept, the present application also proposes an AlV65 alloy, which is prepared based on the following method.

[0037] The vanadium flakes, aluminum particles, AlV65 alloy powder and calcium aluminum alloy are mixed and smelted to obtain AlV65 alloy cake; Shot blasting the AlV65 alloy cake; Crushing the AlV65 alloy cake after shot blasting to obtain AlV65 alloy blocks of a first size and the AlV65 alloy powder; performing sandblasting on the AlV65 alloy block of the first size; The AlV65 alloy block of the first size after sandblasting is crushed for the second time to obtain the AlV65 alloy block of the second size and the AlV65 alloy powder.

[0038] In some embodiments, vanadium flakes, aluminum particles, AlV65 alloy powder, and calcium aluminum alloy are mixed and smelted to obtain an alloy cake, further comprising: Mix 200-220 kg of vanadium flakes, 150-165 kg of aluminum granules, 32-38 kg of cold material, and 1.5-2.5 kg of calcium aluminum alloy.

[0039] In some embodiments, further comprising: Knot the furnace body of the smelting furnace; Place the mixture into the knotted furnace body; An ignition agent is spread over the mixture to cause the mixture to undergo a self-heating reaction.

[0040] In some embodiments, titanium powder is used as an ignition agent.

[0041] In some embodiments, the weight of the titanium powder is 100 g to 250 g.

[0042] In some embodiments, it also includes: White corundum and corundum slag are used to knot the furnace body.

[0043] In some embodiments, the AlV65 alloy cake after shot blasting is crushed once to obtain an AlV65 alloy block of a first size, further comprising: The AlV65 alloy cake is crushed to within 200mm*200mm*200mm.

[0044] In some embodiments, the AlV65 alloy block of the first size after sandblasting is subjected to secondary crushing to obtain an AlV65 alloy block of the second size, further comprising: Crushing the AlV65 alloy block of the first size into pieces of 1-6 mm; The AlV65 alloy blocks of the second size are mixed and mixed evenly, and the mixing time is ≥ 6 min.

[0045] In some embodiments, it also includes: The AlV65 alloy powder obtained from the primary crushing and the secondary crushing is recovered and further smelted.

[0046] The above are exemplary embodiments disclosed in the present invention, but it should be noted that various changes and modifications may be made without departing from the scope disclosed in the embodiments of the present invention as defined in the claims. The functions, steps and / or actions of the method claims according to the disclosed embodiments described herein do not need to be performed in any particular order. In addition, although the elements disclosed in the embodiments of the present invention may be described or required in individual form, they may also be understood as multiple unless explicitly limited to the singular.

[0047] It should be understood that, as used herein, the singular forms "a", "an" are intended to include the plural forms as well, unless the context clearly supports an exception. It should also be understood that, as used herein, "and / or" refers to any and all possible combinations including one or more of the associated listed items.

[0048] The serial numbers of the embodiments disclosed in the above embodiments of the present invention are only for description and do not represent the advantages or disadvantages of the embodiments.

[0049] A person skilled in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other changes in different aspects of the above embodiments of the present invention, which are not provided in detail for the sake of simplicity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention should be included in the protection scope of the embodiments of the present invention.

Claims

1. A method for preparing AlV65 alloy, characterized in that: The following steps are involved: The vanadium flakes, aluminum particles, AlV65 alloy powder and calcium aluminum alloy are mixed and smelted to obtain AlV65 alloy cake; Shot blasting the AlV65 alloy cake; Crushing the AlV65 alloy cake after shot blasting to obtain AlV65 alloy blocks of a first size and the AlV65 alloy powder; performing sandblasting on the AlV65 alloy block of the first size; The AlV65 alloy block of the first size after sandblasting is crushed for the second time to obtain the AlV65 alloy block of the second size and the AlV65 alloy powder.

2. The method according to claim 1, characterized in that The vanadium flakes, aluminum particles, AlV65 alloy powder, and calcium aluminum alloy are mixed and smelted to obtain an alloy cake, further comprising: Mix 200-220 kg of vanadium flakes, 150-165 kg of aluminum granules, 32-38 kg of cold material, and 1.5-2.5 kg of calcium aluminum alloy.

3. The method according to claim 2, characterized in that Also includes; Knot the furnace body of the smelting furnace; Place the mixture into the knotted furnace body; An ignition agent is spread over the mixture to cause the mixture to undergo a self-heating reaction.

4. The method according to claim 3, characterized in that Titanium powder is used as ignition agent.

5. The method according to claim 4, characterized in that The weight of titanium powder is 100g-250g.

6. The method according to claim 3, characterized in that Also includes: White corundum and corundum slag are used to knot the furnace body.

7. The method according to claim 1, characterized in that The AlV65 alloy cake after shot blasting is crushed once to obtain an AlV65 alloy block of a first size, further comprising: The AlV65 alloy cake is crushed to within 200mm*200mm*200mm.

8. The method according to claim 1, characterized in that The AlV65 alloy block of the first size after sandblasting is subjected to secondary crushing to obtain an AlV65 alloy block of the second size, further comprising: Crushing the AlV65 alloy block of the first size into pieces of 1-6 mm; The AlV65 alloy blocks of the second size are mixed and mixed evenly, and the mixing time is ≥ 6 min.

9. The method according to claim 1, characterized in that Also includes: The AlV65 alloy powder obtained from the primary crushing and the secondary crushing is recovered and further smelted.

10. An AlV65 alloy, characterized in that: The AlV65 alloy is prepared based on the method according to any one of claims 1 to 9.

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