Aluminum-tungsten-titanium alloy and preparation method thereof
By using dye clusters as raw materials to prepare aluminum-tungsten-titanium alloy, the problems of decreased catalytic efficiency and secondary pollution caused by the combination of WOx/TiOx catalytic materials and dye molecules were solved, the recycling of dye clusters and the efficient production of alloys were achieved, and the uniformity and quality of the alloy were improved.
Patent Information
- Application Number
- CN202510775681.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-11
- Publication Date
- 2025-09-16
AI Technical Summary
In existing technologies, catalytic materials such as WOx/TiOx combine with dye molecules to form stable "dye clusters", which leads to reduced surface activity of the material, decreased catalytic efficiency, and difficulty in reuse, increasing processing costs and bringing the risk of secondary pollution.
Using dye groups containing WOx and TiOx as raw materials, aluminum tungsten titanium alloy is prepared through oxidation roasting and reduction treatment to achieve the recycling of dye groups. The preparation method includes oxidation roasting, reduction and smelting steps, using a boiling roasting furnace and vacuum suspension melting technology.
The efficient recycling of dye clusters is achieved, secondary pollution is reduced, production costs are lowered, and the problems of excessive slag inclusions and severe element segregation in aluminum-tungsten-titanium alloys are solved, thereby improving the uniformity and quality of the alloy.
Smart Images
Figure CN120648927A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of alloy materials, and particularly relates to the application of a dye group in the preparation of an aluminum-tungsten-titanium alloy, the aluminum-tungsten-titanium alloy and a preparation method thereof. Background Art
[0002] Organic dyes are widely used in textile, leather, printing and dyeing industries. The discharge of wastewater containing organic dyes into the environment poses a serious threat to the ecosystem and human health. x / TiO x Metal oxides such as WO are widely used in dye wastewater treatment due to their excellent photocatalytic properties and adsorption capacity. However, during the treatment process, WO x and TiO x Catalytic materials such as WO 2 and WO 3 combine with dye molecules to form a stable "dye group", which reduces the surface activity of the material, reduces the catalytic efficiency, and even causes the catalyst to fail. x / TiO x The material is difficult to reuse directly, which not only increases the processing cost but also brings the risk of secondary pollution. x / TiO x -Dye clusters have become a difficult problem that needs to be solved urgently. Summary of the Invention
[0003] In view of this, the present invention provides the application of dye group in the preparation of aluminum tungsten titanium alloy, aluminum tungsten titanium alloy and its preparation method. x and TiO x The aluminum-tungsten-titanium alloy is prepared by using the dye group as raw material, which realizes the recycling of the dye group and reduces the secondary pollution of the dye group.
[0004] In order to solve the above technical problems, the present invention provides an application of a dye group in the preparation of aluminum tungsten titanium alloy, wherein the dye group includes WO x 、TiO x and organic dye degradation products.
[0005] Preferably, the organic dye degradation products include one or more of benzene ring compounds, phenolic compounds and aldehyde compounds;
[0006] The WO x and TiO x The molar ratio of WO is 1: (0.7-1.5), the WO x and TiO x The ratio of the total mass to the mass of the dye group is (0.62~0.97):1.
[0007] The present invention also provides a method for preparing an aluminum-tungsten-titanium alloy, comprising the following steps:
[0008] The dye group is oxidized and calcined to obtain a WO3 and TiO2 composite;
[0009] Reducing the WO3 and TiO2 composite in a reducing atmosphere to obtain tungsten-titanium alloy powder;
[0010] The tungsten-titanium alloy powder is mixed with an aluminum source and smelted to obtain an aluminum-tungsten-titanium alloy.
[0011] Preferably, before the oxidative roasting, the method further comprises: drying and then crushing the dye mass;
[0012] The drying temperature is 70-80°C and the drying time is 6-10 hours;
[0013] The average particle size of the pulverized product is 1 to 5 mm, and D50 is 2 to 3 mm.
[0014] Preferably, the temperature of the oxidation roasting is 750-950° C., and the holding time of the oxidation roasting is 0.2-0.5 h;
[0015] The oxidative roasting is carried out in oxygen-enriched air, wherein the volume percentage of oxygen in the oxygen-enriched air is 45-55%;
[0016] The oxidative roasting is carried out in a fluidized bed roasting furnace.
[0017] Preferably, the reducing atmosphere comprises a mixed gas of hydrogen and argon, wherein the volume percentage of hydrogen in the mixed gas of hydrogen and argon is 20 to 50%;
[0018] The reduction temperature is 800-1000° C., and the reduction time is 0.5-1 h.
[0019] Preferably, the aluminum source comprises aluminum beans, and the average particle size of the aluminum beans is 5 to 8 mm;
[0020] The mixing of the tungsten-titanium alloy powder and the aluminum source comprises the following steps: melting the aluminum source to obtain aluminum liquid; adding the tungsten-titanium alloy powder to the aluminum liquid;
[0021] The aluminum element in the aluminum source, WO x and TiO x The molar ratio is (2.2-3.6):1.0:(0.7-1.5);
[0022] The melting is first vacuum suspension melting, the vacuum degree of the first vacuum suspension melting is ≤15 Pa, the melting power of the first vacuum suspension melting is 60-80 kW, and the melting time of the first vacuum suspension melting is 10-20 minutes.
[0023] Preferably, the smelting is carried out in a split-type water-cooled copper crucible;
[0024] The smelting includes a second vacuum suspension melting, a third vacuum suspension melting, a fourth vacuum suspension melting and a fifth vacuum suspension melting performed in sequence;
[0025] The second vacuum suspension melting process has a vacuum degree of ≤15 Pa, a melting power of 120-135 kW, and a melting time of 3-5 min;
[0026] The third vacuum suspension melting process has a vacuum degree of ≤15 Pa, a melting power of 140-160 kW, and a melting time of 4-7 minutes;
[0027] The fourth vacuum suspension melting process has a vacuum degree of ≤50 Pa, a melting power of 170-185 kW, and a melting time of 3-5 min;
[0028] The fifth vacuum suspension melting process has a vacuum degree of ≤50 Pa, a melting power of 195-210 kW, and a melting time of 10-20 min.
[0029] Preferably, after smelting, the process further comprises: water cooling the smelted product, wherein the circulation rate of cooling water for water cooling is 10-15m 3 / h, the pressure of the cooling water is 3-3.5MPa;
[0030] The water inlet temperature of the water cooling is 20-25°C, and the water outlet temperature of the water cooling is 45-50°C.
[0031] The present invention also provides an aluminum-tungsten-titanium alloy prepared by the preparation method described in the above technical solution, comprising the following elemental components in percentage by mass: 55-65wt% tungsten, 10-18wt% titanium, and the remainder aluminum and inevitable impurities.
[0032] The present invention provides a method for preparing aluminum tungsten titanium alloy, comprising the following steps: oxidizing and roasting a dye group to obtain a WO3 and TiO2 composite; reducing the WO3 and TiO2 composite under a reducing atmosphere to obtain a tungsten titanium alloy powder; mixing the tungsten titanium alloy powder with an aluminum source and smelting the mixture to obtain an aluminum tungsten titanium alloy. x / TiO x - Aluminum-tungsten-titanium alloy is prepared using dye clusters and aluminum as raw materials, which realizes the recycling of discarded dye-sensitized photocatalytic materials and reduces secondary pollution from dye clusters. At the same time, the preparation method provided by the present invention solves the problems of excessive slag inclusions and severe element segregation in aluminum-tungsten-titanium alloy produced by the off-furnace method. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] Figure 1Schematic diagram of the structure of the device used to prepare aluminum-tungsten-titanium alloy in an embodiment of the present invention;
[0034] Figure 2 Schematic diagram of the shapes and sampling point positions of the aluminum-tungsten-titanium alloy ingots prepared in Examples 1 to 3;
[0035] Figure 3 Schematic diagram of the shape and sampling point positions of the aluminum-tungsten-titanium alloy ingot prepared in Comparative Example 1;
[0036] Figure 4 This is the metallographic diagram of the aluminum-tungsten-titanium alloy prepared in Example 1;
[0037] Figure 5 This is the metallographic image of the aluminum-tungsten-titanium alloy prepared in Example 2;
[0038] Figure 6 This is the metallographic image of the aluminum-tungsten-titanium alloy prepared in Example 3;
[0039] Figure 7 This is the metallographic diagram of the aluminum-tungsten-titanium alloy prepared in Comparative Example 1. DETAILED DESCRIPTION
[0040] The present invention provides an application of a dye group in the preparation of aluminum tungsten titanium alloy, wherein the dye group includes WO x 、TiO x and organic dye degradation products.
[0041] As a specific embodiment of the present invention, the dye group is derived from discarded dye-sensitized photocatalytic materials; the organic dye degradation products may include one or more of benzene ring compounds, phenolic compounds and aldehyde compounds; the WO x and TiO x The molar ratio of WO can be 1: (0.7 ~ 1.5), specifically 1: 8, 1: 0.96, 1: 1.1, 1: 1.3 or 1: 1.5; the WO x and TiO x The mass ratio of the total mass of the dye group can be (0.62-0.97):1, and can be specifically 0.7:1, 0.84:1, 0.9:1 or 0.97:1.
[0042] The present invention also provides a method for preparing an aluminum-tungsten-titanium alloy, comprising the following steps:
[0043] The dye group is oxidized and calcined to obtain a WO3 and TiO2 composite;
[0044] Reducing the WO3 and TiO2 composite in a reducing atmosphere to obtain tungsten-titanium alloy powder;
[0045] The tungsten-titanium alloy powder is mixed with an aluminum source and smelted to obtain an aluminum-tungsten-titanium alloy.
[0046] The present invention oxidatively roasts the dye mass to obtain a WO3 and TiO2 composite. As a specific embodiment of the present invention, the oxidative roasting process may further include drying and then crushing the dye mass before oxidative roasting. The drying temperature may be 70-80°C, specifically 70°C, 73°C, 75°C, 78°C, or 80°C; the drying time may be 6-10 hours, specifically 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours; the average particle size of the crushed product may be 1-5 mm, specifically 1 mm, 2 mm, 2.4 mm, 3 mm, 4 mm, or 5 mm; and the D50 of the crushed product may be 2-3 mm, specifically 2 mm or 3 mm. The present invention has no special requirements for the crushing process, as long as the desired particle size can be achieved.
[0047] The present invention can fully roast the organic impurities in the dye mass after pulverization, and can also make the WO x and TiO x Fully oxidized.
[0048] As a specific embodiment of the present invention, the temperature of the oxidation roasting can be 750-950°C, specifically 750°C, 800°C, 850°C, 900°C or 950°C; the holding time of the oxidation roasting can be 0.2-0.5h, specifically 0.2h, 0.3h, 0.4h or 0.5h; the oxidation roasting can be carried out in oxygen-enriched air, and the volume percentage of oxygen in the oxygen-enriched air can be 45-55%, specifically 45%, 48%, 50%, 53% or 55%; before the oxidation roasting, the present invention can be vacuumed and then the oxygen-enriched air can be introduced; the vacuum degree of the vacuuming can be no higher than 1.5×10 4 Pa, which can be specifically 1.8×10 3As a specific embodiment of the present invention, the oxidative roasting can be carried out in a fluidized bed roasting furnace; the bottom of the fluidized bed roasting furnace is made of porous bricks; and the surface of the gas pipe of the fluidized bed roasting furnace is wrapped with alumina fiber fabric, which has excellent high temperature resistance and thermal insulation effect. The thickness of the filler subjected to oxidation roasting in the fluidized bed roasting furnace of the present invention can be 300-400 mm, specifically 300 mm, 330 mm, 350 mm, 380 mm or 400 mm; the height of the fluidized bed can be 800-1400 mm, specifically 800 mm, 1000 mm, 1200 mm or 1400 mm; the critical wind speed can be 0.7-1.1 m / s, specifically 0.7 m / s, 0.8 m / s, 0.9 m / s, 1.0 m / s or 1.1 m / s; and the wind pressure can be 800-1000 mmH2O, specifically 800 mmH2O, 900 mmH2O or 1000 mmH2O.
[0049] The present invention performs oxidation roasting in a fluidized bed roasting furnace to put the material in a suspended state, thereby making the roasting more complete and fully oxidizing the material to obtain metal oxides with consistent valence states. At the same time, organic impurities are fully burned and removed from the dye mass.
[0050] As a specific embodiment of the present invention, after the oxidative roasting, the further step may be: cooling the system after the oxidative roasting to room temperature, wherein the room temperature may be 20-35° C., or 25-30° C. The present invention has no special requirements for the cooling method, and conventional methods in the art may be used.
[0051] After obtaining the WO3 and TiO2 composite, the present invention reduces the WO3 and TiO2 composite in a reducing atmosphere to obtain tungsten-titanium alloy powder. As a specific embodiment of the present invention, the reduction can be carried out in a fluidized bed roasting furnace; before the reduction, the further step may be: evacuating the fluidized bed roasting furnace; the vacuum degree of the evacuation can be 1×10 2 ~1×10 3 Pa, specifically 100 Pa, 300 Pa, 500 Pa, 800 Pa or 1000 Pa. When the reduction is carried out in the fluidized bed roasting furnace of the present invention, the boiling layer height can be 700-1200 mm, specifically 700 mm, 800 mm, 900 mm, 1000 mm, 1100 mm or 1200 mm; the critical wind speed can be 0.7-1.1 m / s, specifically 0.7 m / s, 0.8 m / s, 0.9 m / s, 1.0 m / s or 1.1 m / s; the wind pressure can be 800-1000 mmH2O, specifically 800 mmH2O, 900 mmH2O or 1000 mmH2O.
[0052] As a specific embodiment of the present invention, the reducing atmosphere may include a mixture of hydrogen and argon, and the volume percentage of hydrogen in the mixture of hydrogen and argon may be 20-50%, specifically 20%, 30%, 40% or 50%; the reduction temperature may be 800-1000°C, specifically 800°C, 850°C, 900°C, 950°C or 1000°C; the reduction time may be 0.5-1h, specifically 0.5h, 0.8h or 1h.
[0053] After obtaining the tungsten-titanium alloy powder, the present invention mixes the tungsten-titanium alloy powder with an aluminum source and smelts the mixture to obtain an aluminum-tungsten-titanium alloy. As a specific embodiment of the present invention, the mixing of the tungsten-titanium alloy powder and the aluminum source comprises the following steps: melting the aluminum source to obtain aluminum liquid; adding the tungsten-titanium alloy powder to the aluminum liquid;
[0054] As a specific embodiment of the present invention, the aluminum source may include aluminum beans, the average particle size of the aluminum beans may be 5 to 8 mm, specifically 5 mm, 6 mm, 7 mm, or 8 mm; the purity of the aluminum beans may be ≥99.99%.
[0055] As a specific embodiment of the present invention, the aluminum source contains aluminum, WO x and TiO x The molar ratio can be 2.2-3.6:1.0:0.7-1.5, or 2.5-3:1.0:0.9-1.2, and can be specifically 2.54:1:0.96;
[0056] As a specific embodiment of the present invention, the melting can be carried out in a split water-cooled copper crucible; the melting can be a first vacuum suspension melting, and the vacuum degree of the first vacuum suspension melting can be ≤15Pa, and can be specifically 15Pa, 13Pa or 10Pa; the melting power of the first vacuum suspension melting can be 60-80kW, and can be specifically 60kW, 65kW, 70kW, 75kW or 80kW; the melting time of the first vacuum suspension melting can be 10-20min, and can be specifically 10min, 15min or 20min.
[0057] In the present invention, the tungsten-titanium alloy powder has a high melting point and is not easy to melt. After the aluminum is melted, adding the tungsten-titanium alloy powder to the aluminum liquid helps it melt, shortens the smelting time, and reduces the smelting energy consumption.
[0058] As a specific embodiment of the present invention, the smelting can be carried out in a split water-cooled copper crucible; the tungsten-titanium alloy powder can be added to the aluminum liquid in 3 to 5 times, specifically 4 times; vacuum suspension melting is carried out after each addition of the titanium-tungsten alloy powder, and the power of the latter vacuum suspension melting is higher than the power of the previous vacuum suspension melting; taking the addition of the tungsten-titanium alloy powder to the aluminum liquid in 4 times as an example, the smelting includes a second vacuum suspension melting, a third vacuum suspension melting, a fourth vacuum suspension melting and a fifth vacuum suspension melting carried out in sequence. As a specific embodiment of the present invention, the vacuum degree of the second vacuum suspension melting can be ≤15Pa, which can be specifically 15Pa, 13Pa or 10Pa; the melting power can be 120-135kW, which can be specifically 120kW, 125kW, 130kW or 135kW; the melting time can be 3-5min, which can be specifically 3min, 4min or 5min; the vacuum degree of the third vacuum suspension melting can be ≤15Pa, which can be specifically 15Pa, 13Pa or 10Pa; the melting power can be 140-160kW, which can be specifically 140kW, 145kW, 150kW, 155kW or 160kW; the melting time can be 4-7min, which can be specifically 4min, 5min, 6min or 7min; the fourth vacuum The vacuum degree of air suspension melting can be ≤50Pa, and can be specifically 50Pa, 40Pa, 30Pa, 20Pa or 15Pa; the melting power can be 170-185kW, and can be specifically 170kW, 175kW, 180kW, 183kW or 185kW; the melting time can be 3-5min, and can be specifically 3min, 4min or 5min; the vacuum degree of the fifth vacuum suspension melting can be ≤50Pa, and can be specifically 50Pa, 40Pa, 30Pa, 20Pa or 15Pa; the melting power can be 195-210kW, and can be specifically 195kW, 200kW, 205kW, 208kW or 210kW; the melting time can be 10-20min, and can be specifically 10min, 15min or 20min.
[0059] The present invention performs vacuum suspension smelting in steps, which can reduce energy consumption and control raw material burning loss.
[0060] As a specific embodiment of the present invention, the smelting may further include: water cooling the smelted product to obtain aluminum tungsten titanium alloy; As a specific embodiment of the present invention, the present invention performs water cooling in a split-type water-cooled copper crucible. As a specific embodiment of the present invention, the circulation volume of the cooling water for water cooling can be 10 to 15 m 3 / h, which can be specifically 10m 3 / h、12m 3 / h or 15m 3 / h; the cooling water pressure can be 3-3.5MPa, specifically 3MPa, 3.3MPa, or 3.5MPa; the water inlet temperature of the water cooling can be 20-25°C, specifically 20°C, 23°C, or 25°C; the water outlet temperature of the water cooling can be 45-50°C, specifically 45°C, 48°C, or 50°C. The present invention has no special requirements for the water cooling time, as long as an aluminum-tungsten-titanium alloy ingot can be obtained.
[0061] In the present invention, WO x and TiO x The dye groups are mainly derived from discarded dye-sensitized photocatalytic materials. The WO x and TiO x It can be used as one of the components of metal alloys for the preparation of aluminum-tungsten-titanium master alloys, which not only realizes the comprehensive utilization of waste dye groups, but also broadens the selection range of raw materials for aluminum-tungsten-titanium master alloys and greatly reduces production costs.
[0062] Calculated by mass percentage, the aluminum-tungsten-titanium alloy prepared according to the preparation method provided by the present invention includes 55-65wt% tungsten, 10-18wt% titanium, and the remainder aluminum and inevitable impurities; it can be 61-62wt% tungsten, 15-16wt% titanium, and the remainder aluminum and inevitable impurities; calculated by mass percentage, the impurities include: iron ≤0.03wt%, silicon ≤0.04wt%, carbon ≤0.04wt%, oxygen ≤0.03wt%, and nitrogen ≤0.05wt%.
[0063] The aluminum-tungsten-titanium alloy prepared according to the preparation method provided by the present invention contains fewer impurities, has a lower degree of element segregation in the alloy, and has higher uniformity.
[0064] The aluminum-tungsten-titanium alloy provided by the present invention can be used as a raw material to prepare high-temperature titanium alloys such as TC25, which are widely used in key components such as aviation turbine engines and high-temperature gas turbines.
[0065] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0066] The structural diagram of the preparation device used in the embodiment is as follows Figure 1 shown.
[0067] Example 1
[0068] Containing WO x 、TiO x and dye groups of organic dye degradation products (WO x and TiO xThe molar ratio of WO is 1:1.04. x and TiO x The total mass of the dye agglomerate was 0.84:1, and the dye agglomerate was dried at 80°C for 8 hours and then pulverized to obtain particles with an average particle size of 2.4 mm. 58.8 kg of the pulverized dye agglomerate particles were placed in a fluidized bed roasting furnace with a filler thickness of 350 mm. The furnace was closed and a Roots pump was turned on to evacuate to 1.8 × 10 3 After the molten metal is heated to 1000 rpm, oxygen-enriched air with an oxygen volume percentage of 50% is introduced, and power is supplied for oxidation roasting to obtain a WO3 and TiO2 composite. The oxidation roasting conditions are as follows: a boiling layer height of 800 mm, a critical wind speed of 0.8 m / s, a blast pressure of 800 mmH2O, a roasting temperature of 950°C, and a roasting time of 0.5 h.
[0069] The WO3 and TiO2 composite is placed in a fluidized bed roasting furnace, cooled to 30°C, the oxygen-enriched air is turned off, the vacuum is evacuated to 100 Pa, a mixture of hydrogen and argon is introduced, and electric heating is performed for reduction to obtain tungsten-titanium alloy powder; the reduction conditions are as follows: the boiling layer height is controlled to be 700 mm, the critical wind speed is 0.7 m / s, the wind pressure is 800 mmH2O, the reduction temperature is 900°C, the reduction time is 1 hour, the volume fraction of hydrogen in the H2 and Ar mixture is 50%, and the total volume fraction of hydrogen and argon is greater than 99.99%;
[0070] 11 kg (407.4 mol) of aluminum beans (99.99% purity, 6.8 mm average particle size) were placed into a split-type water-cooled copper crucible using an automatic feeding device. After evacuation to 15 Pa, power was supplied for the first vacuum suspension smelting to obtain aluminum liquid. The smelting power was 80 kW and the smelting time was 20 min.
[0071] The tungsten-titanium alloy powder in the fluidized bed roasting furnace is poured into the aluminum liquid in the split-type water-cooled copper crucible by using an automatic dumping device, and the material is evenly added in 4 times. At the same time, the melting power is increased before each feeding, and four vacuum suspension melting processes are performed; the vacuum suspension melting includes the second vacuum suspension melting, the third vacuum suspension melting, the fourth vacuum suspension melting and the fifth vacuum suspension melting in sequence; the vacuum degree of the second vacuum suspension melting is about 15 Pa, the melting power is 120 kW, and the melting time is 5 min; the vacuum degree of the third vacuum suspension melting is about 15 Pa, the melting power is 150 kW, and the melting time is 6 min; the vacuum degree of the fourth vacuum suspension melting is about 50 Pa, the melting power is 180 kW, and the melting time is 5 min; the vacuum degree of the fifth vacuum suspension melting is about 50 Pa, the melting power is 210 kW, and the melting time is 20 min;
[0072] After the smelting is completed, the power is turned off and the cooling water pump is turned on to cool the split-type water-cooled copper crucible to obtain 47.62 kg of aluminum-tungsten-titanium alloy; the water cooling conditions are: the circulation volume of cooling water for water cooling is 10 to 15 m 3 / h, the cooling water pressure is 3~3.5MPa, the water inlet temperature is 20~25℃, and the water outlet temperature is 45~50℃.
[0073] The shape of the obtained aluminum-tungsten-titanium alloy is as follows Figure 2 As shown, Figure 2 The positions indicated by the numbers in the middle are sampling points for sampling. The element composition of the aluminum-tungsten-titanium alloy at different sampling points was tested, and the results are listed in Table 1.
[0074] Table 1 Analysis of the sampling results of the aluminum-tungsten-titanium alloy produced in Example 1
[0075]
[0076] Example 2
[0077] An aluminum tungsten titanium alloy ingot was prepared according to the method of Example 1, except that, instead of placing 58.8 kg of crushed dye agglomerate particles into the boiling roasting furnace, 63.1 kg of crushed dye agglomerate particles were placed into the boiling roasting furnace; and 11 kg (407.4 mol) of aluminum block was subjected to the first vacuum suspension melting, instead of 11.8 kg (437 mol) of aluminum block was subjected to the first vacuum suspension melting. The mass of the obtained aluminum tungsten titanium alloy ingot was 51.30 kg.
[0078] The shape of the aluminum-tungsten-titanium alloy ingot is as follows: Figure 2 As shown, Figure 2 The positions indicated by the numbers in the middle are sampling points for sampling. The element composition of the aluminum-tungsten-titanium alloy at different sampling points was tested, and the results are listed in Table 2.
[0079] Table 2 Analysis of the sampling results of the aluminum-tungsten-titanium alloy produced in Example 2
[0080]
[0081]
[0082] Example 3
[0083] An aluminum tungsten titanium alloy ingot was prepared according to the method of Example 1, except that, instead of placing 58.8 kg of crushed dye agglomerate particles into the boiling roasting furnace, 65.3 kg of crushed dye agglomerate particles were placed into the boiling roasting furnace; and instead of performing the first vacuum suspension melting of 11 kg (407.4 mol) of aluminum block, 12.2 kg (452 mol) of aluminum block was performed the first vacuum suspension melting. The mass of the obtained aluminum tungsten titanium alloy ingot was 53.04 kg.
[0084] The shape of the aluminum-tungsten-titanium alloy ingot is as follows: Figure 2 As shown, Figure 2 The positions indicated by the numbers in the middle are sampling points for sampling. The element composition of the aluminum-tungsten-titanium alloy at different sampling points was tested, and the results are listed in Table 3.
[0085] Table 3 Analysis of the sampling results of the aluminum-tungsten-titanium alloy produced in Example 3
[0086]
[0087]
[0088] It can be seen from the test results in Tables 1 to 3 that the aluminum-tungsten-titanium alloy obtained according to the preparation method provided by the present invention has fewer impurities, and by comparing the results of the elemental composition of different sampling points (range and standard deviation), it can be seen that the degree of element segregation in the prepared aluminum-tungsten-titanium alloy is low.
[0089] Comparative Example 1
[0090] A WO3 and TiO2 composite was prepared according to the method of Example 1 (58.8 kg of crushed dye pellets were oxidatively roasted);
[0091] The prepared WO3 and TiO2 composite and 24.5 kg of aluminum particles with a purity of 99.99% and an average particle size of 1 mm were mixed in a drum mixer at a drum speed of 50 r / min and a mixing time of 15 min.
[0092] A 360×360×115mm reaction crucible was built with magnesia bricks as refractory material, a graphite furnace body was placed outside the crucible, and the crucible was placed in the center of the graphite furnace body, and the gap between the furnace body and the crucible was filled with magnesia sand.
[0093] The mixed raw materials were placed in a crucible, ignited by a magnesium rod, cooled to 25°C, and then slag was removed to obtain 44.53 kg of aluminum-tungsten-titanium alloy ingots.
[0094] The shape of the aluminum-tungsten-titanium alloy ingot is as follows: Figure 3 As shown, Figure 3 The positions indicated by the numbers in the middle are sampling points for sampling. The element composition of the aluminum-tungsten-titanium alloy at different sampling points was tested, and the results are listed in Table 4.
[0095] Table 4 Analysis of the sampling results of the aluminum-tungsten-titanium alloy produced in Comparative Example 1
[0096]
[0097]
[0098] The aluminum-tungsten-titanium alloys prepared in Examples 1 to 3 and Comparative Example 1 were subjected to metallographic observation to obtain metallographic diagrams, as shown in FIG. Figures 4 to 7 As shown, Figure 4 This is a metallographic image of the aluminum-tungsten-titanium alloy ingot prepared in Example 1; Figure 5 This is a metallographic image of the aluminum-tungsten-titanium alloy ingot prepared in Example 2; Figure 6 This is a metallographic image of the aluminum-tungsten-titanium alloy ingot prepared in Example 3; Figure 7 This is the metallographic image of the aluminum-tungsten-titanium alloy ingot prepared in Comparative Example 1.
[0099] Combined with the element analysis results in Tables 1 to 4 and Figures 4 to 7 It can be seen from the metallographic diagram that, compared with the thermite method (Comparative Example 1), the aluminum tungsten titanium alloy prepared according to the method provided by the present invention has higher uniformity, effectively solves the element segregation problem of the aluminum tungsten titanium alloy, and has low impurity content and pure alloy metallographic structure, which greatly improves the quality of the aluminum tungsten titanium alloy.
[0100] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.
Claims
1. The application of dye group in the preparation of aluminum tungsten titanium alloy is characterized in that: The dye group includes WO x 、TiO x and organic dye degradation products.
2. The application according to claim 1, characterized in that The organic dye degradation products include one or more of benzene ring compounds, phenolic compounds and aldehyde compounds; The WO x and TiO x The molar ratio of WO is 1: (0.7-1.5), the WO x and TiO x The ratio of the total mass to the mass of the dye group is (0.62~0.97):
1.
3. A method for preparing an aluminum-tungsten-titanium alloy, characterized in that: The following steps are involved: The dye group is oxidized and calcined to obtain a WO3 and TiO2 composite; Reducing the WO3 and TiO2 composite in a reducing atmosphere to obtain tungsten-titanium alloy powder; The tungsten-titanium alloy powder is mixed with an aluminum source and smelted to obtain an aluminum-tungsten-titanium alloy.
4. The preparation method according to claim 3, characterized in that Before the oxidative roasting, the further step includes: drying and then crushing the dye mass; The drying temperature is 70-80°C and the drying time is 6-10 hours; The average particle size of the pulverized product is 1 to 5 mm, and D50 is 2 to 3 mm.
5. The preparation method according to claim 3 or 4, characterized in that: The temperature of the oxidation roasting is 750-950° C., and the holding time of the oxidation roasting is 0.2-0.5 h; The oxidative roasting is carried out in oxygen-enriched air, wherein the volume percentage of oxygen in the oxygen-enriched air is 45-55%; The oxidative roasting is carried out in a fluidized bed roasting furnace.
6. The preparation method according to claim 3, characterized in that: The reducing atmosphere comprises a mixed gas of hydrogen and argon, wherein the volume percentage of hydrogen in the mixed gas of hydrogen and argon is 20 to 50%; The reduction temperature is 800-1000° C., and the reduction time is 0.5-1 h.
7. The preparation method according to claim 3, characterized in that: The aluminum source includes aluminum beans, and the average particle size of the aluminum beans is 5 to 8 mm; The mixing of the tungsten-titanium alloy powder and the aluminum source comprises the following steps: melting the aluminum source to obtain aluminum liquid; adding the tungsten-titanium alloy powder to the aluminum liquid; The aluminum element in the aluminum source, WO x and TiO x The molar ratio is (2.2-3.6):1.0:(0.7-1.5); The melting is first vacuum suspension melting, the vacuum degree of the first vacuum suspension melting is ≤15 Pa, the melting power of the first vacuum suspension melting is 60-80 kW, and the melting time of the first vacuum suspension melting is 10-20 minutes.
8. The preparation method according to claim 3, characterized in that: The smelting is carried out in a split-type water-cooled copper crucible; The smelting includes a second vacuum suspension melting, a third vacuum suspension melting, a fourth vacuum suspension melting and a fifth vacuum suspension melting performed in sequence; The second vacuum suspension melting process has a vacuum degree of ≤15 Pa, a melting power of 120-135 kW, and a melting time of 3-5 min; The third vacuum suspension melting process has a vacuum degree of ≤15 Pa, a melting power of 140-160 kW, and a melting time of 4-7 minutes; The fourth vacuum suspension melting process has a vacuum degree of ≤50 Pa, a melting power of 170-185 kW, and a melting time of 3-5 min; The fifth vacuum suspension melting process has a vacuum degree of ≤50 Pa, a melting power of 195-210 kW, and a melting time of 10-20 min.
9. The preparation method according to claim 3 or 8, characterized in that: After the smelting, the smelted product is further cooled by water, and the circulation volume of the cooling water is 10-15m 3 / h, the pressure of the cooling water is 3-3.5MPa; The water inlet temperature of the water cooling is 20-25°C, and the water outlet temperature of the water cooling is 45-50°C.
10. The aluminum-tungsten-titanium alloy prepared by the preparation method according to any one of claims 3 to 9, characterized in that: The invention comprises the following element components in percentage by mass: 55-65 wt% of tungsten, 10-18 wt% of titanium, and the balance of aluminum and inevitable impurities.