CN113388756A - Preparation method of multi-element reinforced high-temperature titanium-based composite material - Google Patents

Preparation method of multi-element reinforced high-temperature titanium-based composite material Download PDF

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CN113388756A
CN113388756A CN202110713174.2A CN202110713174A CN113388756A CN 113388756 A CN113388756 A CN 113388756A CN 202110713174 A CN202110713174 A CN 202110713174A CN 113388756 A CN113388756 A CN 113388756A
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alloy
aluminum
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titanium
based composite
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CN113388756B (en
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徐丽娟
郑云飞
梁振泉
肖树龙
田竟
陈玉勇
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1005—Pretreatment of the non-metallic additives
    • C22C1/1015—Pretreatment of the non-metallic additives by preparing or treating a non-metallic additive preform
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1094—Alloys containing non-metals comprising an after-treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Abstract

The invention discloses a preparation method of a multielement enhanced high-temperature titanium-based composite material, and relates to the field of preparation methods of multielement enhanced high-temperature titanium-based composite materials. The invention aims to solve the problem that the existing high-temperature titanium alloy silicide is not uniformly precipitated and is easy to grow up to cause high-temperature performance deterioration. The method comprises the following steps: pretreating the raw materials, and weighing; pressing an alloy block and a secondary feeding block; preheating; smelting; and (6) heat treatment. The invention uses reinforcing phases of TiB, TiC and Y2O3The uniform distribution of the silicide is realized, and the growth of the silicide can be inhibited by the reinforcing phase, thereby further improving the uniformity of the silicideImprove the creep resistance of the alloy. The method is used for preparing the multielement reinforced high-temperature titanium-based composite material.

Description

Preparation method of multi-element reinforced high-temperature titanium-based composite material
Technical Field
The invention relates to the field of preparation methods of multi-element reinforced high-temperature titanium-based composite materials.
Background
The titanium-based composite material (TMCs) has higher specific strength and high temperature resistance, and has wide application prospect in the fields of aviation, aerospace, automobile industry and the like. The titanium-based composite material can remarkably increase the tensile strength by adding the reinforcing phase. However, if the bonding effect between the reinforcing phase and the matrix is poor, the reinforcing phase is peeled off or debonded during deformation, and the mechanical properties of the titanium-based composite material are easily deteriorated. Therefore, in selecting the reinforcing phase, the difference in physical properties between the reinforcing phase and the matrix, particularly the difference in thermal expansion coefficient, is a priority. TiB and TiC have similar density and thermal expansion coefficient with titanium matrix, high elastic modulus and hardness and excellent thermal stability, and are considered as the optimal reinforcing phase of the titanium matrix composite material. Y is2O3The material has the advantages of high melting point and good high-temperature thermal stability, can effectively improve the creep resistance of the material, and is also an ideal reinforcing phase. Research shows that trace TiB, TiC and Y2O3The additive can form component supercooling at the front edge of a solid-liquid interface, promote beta-Ti nucleation and growth, obviously refine crystal grains and be beneficial to improving the mechanical property of the material. Therefore, TiB, TiC and Y are selected2O3It is possible from the viewpoint of composition design as the reinforcing phase.
In high temperature titanium-based composites, small amounts of Si are typically added to the matrix composition in order to increase the creep resistance of the material. Si generally exists in a solid solution state, and a large amount of silicide is often precipitated in the long-term thermal exposure or aging process, and the silicide has a strong pinning effect on dislocation, so that the slippage and climbing of the dislocation are hindered, and the creep resistance of the alloy is improved. However, these silicides are mainly distributed on the α/β interface, are not uniformly distributed, and are prone to growth and coarsening, which can seriously affect the plasticity of the material. For high-temperature titanium-based composite materials, the addition of the reinforcing phase can refine the tissues and improve the strength of the materials, but can also reduce the plasticity of the materials. If the precipitation behavior of the silicide cannot be well controlled, the plasticity of the material will be further deteriorated, which is not favorable for the long-term use of the material in a high-temperature environment.
Current silicide control approaches focus on heat treatment and hot working, which are costly, complex to operate, and often require long-term aging. In the high-temperature titanium-based composite material, the reinforced phase can obviously block dislocation, so that a high-density dislocation area is formed, and nucleation and precipitation of silicide are promoted. Therefore, by regulating the addition amount of the reinforcing phase and utilizing the synergistic effect of the silicide and the reinforcing phase, the distribution condition of the silicide can be improved and the growth of the silicide can be limited, so that the method is a method for controlling the form and the distribution of the silicide, and is simple and convenient to operate. There is no report of controlling silicide characteristics by controlling the content of the enhancement phase.
Disclosure of Invention
The invention provides a preparation method of a multielement reinforced high-temperature titanium-based composite material, aiming at solving the problems that the existing high-temperature titanium alloy silicide is not uniformly precipitated and is easy to grow up to cause the deterioration of high-temperature performance.
A preparation method of a multi-element reinforced high-temperature titanium-based composite material specifically comprises the following steps:
firstly, carrying out ultrasonic cleaning on a titanium rod, high-purity aluminum and high-purity tin in alcohol, and drying;
secondly, according to the weight percentage of the elements: 5-6% of Al, 2-5% of Sn, 2-8% of Zr, 0.6-1.0% of Mo, less than or equal to 1% of W, less than or equal to 1% of Nb, 0.25-0.45% of Si and the balance of Ti, and titanium sponge, zirconium sponge, high-purity silicon, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, aluminum-niobium intermediate alloy, the titanium rod treated in the first step, high-purity aluminum and high-purity tin are weighed;
according to the volume percentage of the reinforcing phase: 1 to 2 percent of TiB and 1 to 2 percent of TiC, and weighing B4Powder C and powder C;
thirdly, pressing the titanium sponge, the high-purity aluminum, the zirconium sponge, the high-purity tin, the high-purity silicon, the aluminum-molybdenum intermediate alloy, the aluminum-tungsten intermediate alloy, the aluminum-niobium intermediate alloy and the C powder which are weighed in the second step into a plurality of alloy blocks; the alloy block sequentially comprises titanium sponge, zirconium sponge, aluminum-niobium intermediate alloy, C powder, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, high-purity tin, high-purity silicon and high-purity aluminum from bottom to top; wherein the powder C is wrapped by aluminum foil;
fourthly, B weighed in the second step4Wrapping the powder C by using aluminum foil, and pressing into a plurality of secondary feeding blocks;
fifthly, preheating: preheating the steel die, the alloy block prepared in the third step and the secondary feeding block prepared in the fourth step;
sixthly, smelting:
cleaning the interior of a water-cooled copper crucible and a secondary charging hopper;
uniformly spreading granular titanium sponge at the bottom of the water-cooled copper crucible; vertically placing a titanium rod in the middle of a water-cooled copper crucible, uniformly placing the alloy blocks processed in the fifth step around the titanium rod, placing the secondary feeding block into a secondary feeding hopper, and closing a furnace door of the vacuum induction smelting furnace;
starting a vacuum pump to vacuumize the vacuum induction melting furnace until the pressure reaches below 5Pa, and filling argon until the internal pressure is 80% -90% of the external pressure; opening a water cooling machine;
fourthly, repeating the step III for 1-3 times, and filling argon into the furnace;
starting a power supply, loading the power to 30-40 kW, and keeping for 5-10 min; then, loading power at the speed of 5kW/min to 7.5kW/min until the power is 60kW to 70kW, keeping for 5min to 10min, and completely melting the materials in the furnace;
sixthly, adding the secondary feeding block to the middle of the crucible through a secondary feeding hopper, loading power at the speed of 10-20 kW/min until the power is 75-90 kW, stirring at a high speed of 800-1000 rpm for 3-5 min, and then stirring at a low speed of 300-500 rpm for 5-10 min to obtain a refined alloy melt;
seventhly, overturning the water-cooled copper crucible by 160 degrees, pouring the alloy melt into a steel mold, turning off an induction melting power supply, cooling in the furnace for 30-40 min, introducing argon, opening a furnace door, and taking out an alloy ingot in the steel mold;
seventhly, heat treatment: and carrying out homogenizing annealing treatment on the alloy ingot obtained in the sixth step at 650-700 ℃ to obtain the multi-element reinforced high-temperature titanium-based composite material.
Furthermore, in the second step, the mass content of Mo in the aluminum-molybdenum intermediate alloy is 50.5%, the mass content of W in the aluminum-tungsten intermediate alloy is 57.44%, and the mass content of Nb in the aluminum-niobium intermediate alloy is 83.15%.
Furthermore, nano Y is also added into the reinforcing phase in the second step2O3Powder of Y2O3The volume percentage of the component (B) is less than or equal to 0.5.
When the reinforcing phase is nano Y2O3When the powder is prepared, step four, weighing the B4C powder and nano-Y2O3And uniformly mixing the powder, wrapping the powder by using an aluminum foil, and pressing the powder into a plurality of secondary feeding blocks.
Because titanium is adhered to the bottom of the crucible in the smelting process, the granular titanium sponge is uniformly paved on the bottom of the water-cooled copper crucible in the smelting process, so that the finally obtained composite material has more accurate components.
The matrix is based on a Ti-Al-Sn-Zr-Mo-W-Nb-Si system, and the reinforcing phases are TiB, TiC and Y2O3In order to prevent the plasticity of the material from being too low, the addition amount of the reinforcing phase is limited to 2-4.5%.
The reinforcing phase comprises the following components in percentage: 1-2 Vol% for TiB, 1-2 Vol% for TiC, Y2O3Is less than or equal to 0.5 Vol.%. Wherein TiB and TiC are reacted by 5Ti + B4C4 TiB + TiC and Ti + C TiC, Y2O3By adding nano-Y2O3Adding the powder. By adjusting B4C powder, C powder and nano Y2O3The proportion of the reinforcing phase can be freely changed by adding the powder.
Aggregation and growth of the powder easily occur during smelting, in order to avoid the generation of coarse Y2O3Reinforcing phase, the invention selects nanometer Y2O3Powders are more suitable as starting materials.
Because the melting points of aluminum and tin are low, burning loss in the smelting process is serious, and 2 wt.% of aluminum and 5 wt.% of tin are additionally added in the ingredients.
In the invention, the C powder is a main source of TiC, the addition amount of the C powder is larger, the density is smaller, and if the C powder is directly added into a melt, the C powder is easy to float upwards and is not beneficial to the generation of TiC. In addition, B is4The direct addition of the powder C to the melt can cause an increase in melt viscosity, which is detrimental to melting. Therefore, it will be wrapped with aluminum foil (thickness 0.006 mm).
The cast structure of the titanium-based composite material obtained by the invention is basket structure, and TiB, TiC and Y are obtained2O3The reinforcing phase and the matrix are well combined, the combined interface is smooth, and the silicide is characterized in that: silicide distributed on alpha/beta interface and TiB, TiC, Y2O3The reinforcing phase is in the shape of an ellipsoid or a rod around the reinforcing phase, and the size of the reinforcing phase is 50-300 nm.
The invention has the beneficial effects that:
(1) by using Ti-B4C-C reaction system, in-situ self-generation to obtain TiB and TiC reinforcing phase, Y2O3The heat preservation time is short by adding the materials in the second feeding, and the agglomeration and the growth of the nano powder are effectively prevented. Ti-TiB2Compared with a-C reaction system, the system has the advantages of low raw material cost and easy regulation and control of the proportion of the reinforcing phase.
(2) TiB, TiC and Y2O3The reinforced phase can obviously block the movement of dislocation, form a high-density dislocation area and promote the nucleation and the precipitation of silicide. Silicides in TiB, TiC and Y2O3The intensive precipitation of silicide on the alpha/beta interface is weakened by the massive precipitation around the enhanced phase. The uniform distribution of silicide is realized through the homogenization of the reinforcing phase, so that the creep resistance of the alloy is further improved.
(3) TiB, TiC and Y2O3The growth of silicide around the reinforcing phase is limited, the diffusion of atoms can only be carried out from one side, and the silicide is mainly fine needle-shaped silicide (the long axis dimension is 30-80 nm). Compared with the coarse ellipsoidal silicide (with the major axis size of 150-200 nm) on the alpha/beta interface, the fine silicide resists the dislocation slip climbThe effect is stronger, and the creep resistance of the material is more favorably improved.
The method is used for preparing the multielement reinforced high-temperature titanium-based composite material.
Drawings
FIG. 1 is an SEM photograph of a multi-component reinforced high temperature titanium-based composite material obtained in the first example;
FIG. 2 is a TEM photograph (α/β interface) of the multi-component reinforced high temperature Ti-based composite material obtained in example II after creep for 50h at 650 ℃/140 MPa;
FIG. 3 is a TEM photograph (α/β interface) of the multi-component reinforced high temperature Ti-based composite material obtained in example III after creep for 50h at 650 ℃/140 MPa;
FIG. 4 is a TEM photograph of the multielement enhanced high temperature titanium-based composite material obtained in example three after creeping for 50h under 650 ℃/140MPa (TiB and its surrounding silicide morphology);
FIG. 5 is a TEM photograph of the multielement reinforced high temperature titanium-based composite material obtained in example three after creep for 50h under the condition of 650 ℃/140MPa (Y)2O3And its surrounding silicide topography).
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the multielement reinforced high-temperature titanium-based composite material comprises the following steps:
firstly, carrying out ultrasonic cleaning on a titanium rod, high-purity aluminum and high-purity tin in alcohol, and drying;
secondly, according to the weight percentage of the elements: 5-6% of Al, 2-5% of Sn, 2-8% of Zr, 0.6-1.0% of Mo, less than or equal to 1% of W, less than or equal to 1% of Nb, 0.25-0.45% of Si and the balance of Ti, and titanium sponge, zirconium sponge, high-purity silicon, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, aluminum-niobium intermediate alloy, the titanium rod treated in the first step, high-purity aluminum and high-purity tin are weighed;
according to the volume percentage of the reinforcing phase: 1 to 2 percent of TiB and 1 to 2 percent of TiC, and weighing B4Powder C and powder C;
thirdly, pressing the titanium sponge, the high-purity aluminum, the zirconium sponge, the high-purity tin, the high-purity silicon, the aluminum-molybdenum intermediate alloy, the aluminum-tungsten intermediate alloy, the aluminum-niobium intermediate alloy and the C powder which are weighed in the second step into a plurality of alloy blocks; the alloy block sequentially comprises titanium sponge, zirconium sponge, aluminum-niobium intermediate alloy, C powder, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, high-purity tin, high-purity silicon and high-purity aluminum from bottom to top; wherein the powder C is wrapped by aluminum foil;
fourthly, B weighed in the second step4Wrapping the powder C by using aluminum foil, and pressing into a plurality of secondary feeding blocks;
fifthly, preheating: preheating the steel die, the alloy block prepared in the third step and the secondary feeding block prepared in the fourth step;
sixthly, smelting:
cleaning the interior of a water-cooled copper crucible and a secondary charging hopper;
uniformly spreading granular titanium sponge at the bottom of the water-cooled copper crucible; vertically placing a titanium rod in the middle of a water-cooled copper crucible, uniformly placing the alloy blocks processed in the fifth step around the titanium rod, placing the secondary feeding block into a secondary feeding hopper, and closing a furnace door of the vacuum induction smelting furnace;
starting a vacuum pump to vacuumize the vacuum induction melting furnace until the pressure reaches below 5Pa, and filling argon until the internal pressure is 80% -90% of the external pressure; opening a water cooling machine;
fourthly, repeating the step III for 1-3 times, and filling argon into the furnace;
starting a power supply, loading the power to 30-40 kW, and keeping for 5-10 min; then, loading power at the speed of 5kW/min to 7.5kW/min until the power is 60kW to 70kW, keeping for 5min to 10min, and completely melting the materials in the furnace;
sixthly, adding the secondary feeding block to the middle of the crucible through a secondary feeding hopper, loading power at the speed of 10-20 kW/min until the power is 75-90 kW, stirring at a high speed of 800-1000 rpm for 3-5 min, and then stirring at a low speed of 300-500 rpm for 5-10 min to obtain a refined alloy melt;
seventhly, overturning the water-cooled copper crucible by 160 degrees, pouring the alloy melt into a steel mold, turning off an induction melting power supply, cooling in the furnace for 30-40 min, introducing argon, opening a furnace door, and taking out an alloy ingot in the steel mold;
seventhly, heat treatment: and carrying out homogenizing annealing treatment on the alloy ingot obtained in the sixth step at 650-700 ℃ to obtain the multi-element reinforced high-temperature titanium-based composite material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and step two, the mass content of Mo in the aluminum-molybdenum intermediate alloy is 50.5%, the mass content of W in the aluminum-tungsten intermediate alloy is 57.44%, and the mass content of Nb in the aluminum-niobium intermediate alloy is 83.15%. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the second step, nano Y is also added into the reinforcing phase2O3Powder of Y2O3The volume percentage of the component (B) is less than or equal to 0.5. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: when the reinforcing phase is nano Y2O3When the powder is prepared, step four, weighing the B4C powder and nano-Y2O3And uniformly mixing the powder, wrapping the powder by using an aluminum foil, and pressing the powder into a plurality of secondary feeding blocks. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and step three and step four, the thickness of the aluminum foil is 0.006 mm. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step three, the diameter of the alloy block is 20-30 mm, and the height of the alloy block is 40-50 mm. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and fourthly, the diameter of the secondary feeding block is 5-10 mm, and the height of the secondary feeding block is 10-20 mm. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: step five, controlling the preheating temperature of the mold to be 200-500 ℃ and the preheating time to be 1 h. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and fifthly, controlling the preheating temperature of the alloy block to be 50-200 ℃ and the preheating time to be 1 h. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and fifthly, controlling the preheating temperature of the secondary feeding block to be 50-300 ℃ and the preheating time to be 30 min. The other is the same as one of the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the preparation method of the multielement reinforced high-temperature titanium-based composite material comprises the following steps:
firstly, carrying out ultrasonic cleaning on a titanium rod, high-purity aluminum and high-purity tin in alcohol, and drying;
secondly, according to the weight percentage of the elements: 6% of Al, 4% of Sn, 8% of Zr, 0.8% of Mo, 1% of W, 1% of Nb, 0.25% of Si and the balance of Ti, and weighing titanium sponge, zirconium sponge, high-purity silicon, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, aluminum-niobium intermediate alloy, the titanium rod treated in the step one, high-purity aluminum and high-purity tin;
according to the volume percentage of the reinforcing phase: 1% of TiB, 1% of TiC and Y2O3To 0.3%, weigh B4C powder, Nano Y2O3Powder and powder C;
thirdly, pressing the titanium sponge, the high-purity aluminum, the zirconium sponge, the high-purity tin, the high-purity silicon, the aluminum-molybdenum intermediate alloy, the aluminum-tungsten intermediate alloy, the aluminum-niobium intermediate alloy and the C powder which are weighed in the second step into a plurality of alloy blocks; the alloy block sequentially comprises titanium sponge, zirconium sponge, aluminum-niobium intermediate alloy, C powder, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, high-purity tin, high-purity silicon and high-purity aluminum from bottom to top; wherein the powder C is wrapped by aluminum foil;
fourthly, B weighed in the second step4C powder and nano-Y2O3Wrapping the powder with aluminum foil, and pressing into a plurality of secondary feeding blocks;
fifthly, preheating: preheating the die, the alloy block prepared in the third step and the secondary feeding block prepared in the fourth step;
sixthly, smelting:
cleaning the interior of a water-cooled copper crucible and a secondary charging hopper to ensure that the interior is pollution-free, opening a water-cooled machine, checking whether a water-cooled device leaks water, and closing the water-cooled machine after the water-cooled device is checked;
uniformly spreading 25g of granular titanium sponge at the bottom of the water-cooled copper crucible; vertically placing a titanium rod in the middle of a water-cooled copper crucible, uniformly placing the alloy blocks processed in the fifth step around the titanium rod, placing the secondary feeding block into a secondary feeding hopper, and closing a furnace door of the vacuum induction smelting furnace;
starting a vacuum pump to vacuumize the vacuum induction melting furnace until the pressure reaches below 5Pa, filling argon until the pressure reaches 800Pa, and opening a water cooling machine;
fourthly, repeating the step III for 3 times, and filling argon into the furnace;
starting a power supply, loading the power to 32kW, and keeping for 5 min; then, loading power at the speed of 5kW/min until the power is 60kW, keeping for 5min, and completely melting the materials in the furnace;
sixthly, adding the secondary feeding block to the middle of the crucible through a secondary feeding hopper, loading power at the speed of 10kW/min till the power is 75kW, preventing aggregation of large particles, stirring at a high speed of 800rpm for 3min, promoting uniform dispersion of the reinforcing phase, and stirring at a low speed of 300rpm for 5min to obtain a refined alloy melt;
seventhly, overturning the water-cooled copper crucible by 160 degrees, pouring the alloy melt into a steel mold, turning off an induction melting power supply, cooling in the furnace for 30min, introducing argon, opening a furnace door, and taking out the alloy ingot in the steel mold;
seventhly, heat treatment: and carrying out homogenizing annealing treatment on the alloy ingot obtained in the sixth step at 650 ℃ to obtain the multi-element reinforced high-temperature titanium-based composite material.
The content of the reinforcing phase of the multi-element reinforced high-temperature titanium-based composite material obtained in the embodiment is 1 Vol.% TiB +1 Vol.% TiC +0.3 Vol.% Y2O3。
The SEM photograph of the multielement reinforced high temperature titanium-based composite material obtained in this example is shown in FIG. 1, and it can be seen that the microstructure of the material is basket tissue (black is alpha phase, and white is beta phase). The whisker-shaped reinforcing phase with different lengths is TiB, the equiaxial or strip-shaped reinforcing phase is TiC, and the white granular or rodlike reinforcing phase is Y2O3. The reinforced phase is uniformly separated out and has no segregation phenomenon.
Example two:
the difference between the present embodiment and the first embodiment is:
step two, according to the volume percentage of the enhanced phase: 1.25 percent of TiB and 1.25 percent of TiC, and weighing B4Powder C and powder C;
step six, smelting:
cleaning the interior of a water-cooled copper crucible and a secondary charging hopper to ensure that the interior is pollution-free, opening a water-cooled machine, checking whether a water-cooled device leaks water, and closing the water-cooled machine after the water-cooled device is checked;
uniformly spreading 25g of granular titanium sponge at the bottom of the water-cooled copper crucible; vertically placing a titanium rod in the middle of a water-cooled copper crucible, uniformly placing the alloy blocks processed in the fifth step around the titanium rod, placing the secondary feeding block into a secondary feeding hopper, and closing a furnace door of the vacuum induction smelting furnace;
starting a vacuum pump to vacuumize the vacuum induction melting furnace until the pressure reaches below 5Pa, filling argon until the pressure reaches 800Pa, and opening a water cooling machine;
fourthly, repeating the step III for 3 times, and filling argon into the furnace;
starting a power supply, loading the power to 35kW, and keeping for 4 min; then, loading power at the speed of 5kW/min until the power is 60kW, keeping for 5min, and completely melting the materials in the furnace;
sixthly, adding the secondary feeding block to the middle of the crucible through a secondary feeding hopper, loading power at a speed of 15kW/min until the power is 80kW, preventing aggregation of large particles, stirring at a high speed of 900rpm for 4min, promoting uniform dispersion of the reinforcing phase, and stirring at a low speed of 300rpm for 5min to obtain a refined alloy melt;
and seventhly, overturning the water-cooled copper crucible by 160 degrees, pouring the alloy melt into a steel mold, turning off an induction melting power supply, cooling in the furnace for 40min, introducing argon, opening a furnace door, and taking out the alloy ingot in the steel mold.
The content of the reinforcing phase of the multi-element reinforced high-temperature titanium-based composite material obtained in the embodiment is 1.25 Vol.% TiB +1.25 Vol.% TiC.
And (3) performing a unidirectional constant-load tensile creep test at 650 ℃/140MPa by using an RDL100 creep testing machine, and performing TEM analysis on the creep deformation region tissue after the test is performed for 50 h.
The TEM photograph (alpha/beta interface) of the multielement reinforced high temperature titanium-based composite material obtained in this example after creeping for 50h under the condition of 650 ℃/140MPa is shown in FIG. 2.
Example three:
the difference between the present embodiment and the first embodiment is:
step two, according to the volume percentage of the enhanced phase: 1.25% of TiB, 1.25% of TiC and Y2O3To 0.5%, weigh B4C powder, Nano Y2O3Powder and powder C;
step six, smelting:
cleaning the interior of a water-cooled copper crucible and a secondary charging hopper to ensure that the interior is pollution-free, opening a water-cooled machine, checking whether a water-cooled device leaks water, and closing the water-cooled machine after the water-cooled device is checked;
uniformly spreading 25g of granular titanium sponge at the bottom of the water-cooled copper crucible; vertically placing a titanium rod in the middle of a water-cooled copper crucible, uniformly placing the alloy blocks processed in the fifth step around the titanium rod, placing the secondary feeding block into a secondary feeding hopper, and closing a furnace door of the vacuum induction smelting furnace;
starting a vacuum pump to vacuumize the vacuum induction melting furnace until the pressure reaches below 5Pa, filling argon until the pressure reaches 800Pa, and opening a water cooling machine;
fourthly, repeating the step III for 3 times, and filling argon into the furnace;
starting a power supply, loading the power to 35kW, and keeping for 6 min; then, loading power at the speed of 5kW/min until the power is 60kW, keeping for 5min, and completely melting the materials in the furnace;
sixthly, adding the secondary feeding block to the middle of the crucible through a secondary feeding hopper, loading power at a speed of 15kW/min until the power is 80kW, preventing aggregation of large particles, stirring at a high speed of 5min and a high stirring speed of 1000rpm, promoting uniform dispersion of an enhanced phase, and stirring at a low speed of 5min and a low stirring speed of 400rpm to obtain a refined alloy melt;
and seventhly, overturning the water-cooled copper crucible by 160 degrees, pouring the alloy melt into a steel mold, turning off an induction melting power supply, cooling in the furnace for 40min, introducing argon, opening a furnace door, and taking out the alloy ingot in the steel mold.
The content of the reinforcing phase of the multi-element reinforced high-temperature titanium-based composite material obtained in the embodiment is 1.25 Vol.% TiB +1.25 Vol.% TiC +0.5 Vol.% Y2O3。
And (3) performing a unidirectional constant-load tensile creep test at 650 ℃/140MPa by using an RDL100 creep testing machine, and performing TEM analysis on the creep deformation region tissue after the test is performed for 50 h.
The TEM photograph (alpha/beta interface) of the multielement reinforced high temperature titanium-based composite material obtained in this example after creeping for 50h under the condition of 650 ℃/140MPa is shown in FIG. 3.
As can be seen from FIGS. 2 and 3, for no Y addition2O3The size of the long axis of the coarse silicide close to the alpha/beta interface of the composite material is 150-200 nm, and the long axis direction of the coarse silicide is almost uniformly distributed. For addition of Y2O3The silicide of the composite material is obviously refined, and the long axis dimension is 30-80 nm.
The TEM photograph (TiB and its surrounding silicide morphology) of the multielement enhanced high temperature titanium-based composite material obtained in this example after creeping for 50h under 650 ℃/140MPa is shown in FIG. 4.
TEM photograph (Y) of the multielement enhanced high temperature titanium-based composite material obtained in the embodiment after 50h creep at 650 ℃/140MPa2O3And its surrounding silicide topography) as shown in fig. 5.
As can be seen from FIGS. 4 and 5, TiB and Y2O3Has strong inhibiting effect on dislocation and promotes the precipitation of silicide. TiB and Y2O3The surrounding silicide sizes are not significantly different. The silicide around the TiB is denser, indicating that TiB has a stronger silicide promoting effect. The above results indicate that Y can be used2O3And the interaction of TiB and silicide realizes the uniform precipitation of silicide.

Claims (10)

1. The preparation method of the multielement reinforced high-temperature titanium-based composite material is characterized by comprising the following steps of:
firstly, carrying out ultrasonic cleaning on a titanium rod, high-purity aluminum and high-purity tin in alcohol, and drying;
secondly, according to the weight percentage of the elements: 5-6% of Al, 2-5% of Sn, 2-8% of Zr, 0.6-1.0% of Mo, less than or equal to 1% of W, less than or equal to 1% of Nb, 0.25-0.45% of Si and the balance of Ti, and titanium sponge, zirconium sponge, high-purity silicon, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, aluminum-niobium intermediate alloy, the titanium rod treated in the first step, high-purity aluminum and high-purity tin are weighed;
according to the volume percentage of the reinforcing phase: 1 to 2 percent of TiB and 1 to 2 percent of TiC, and weighing B4Powder C and powder C;
thirdly, pressing the titanium sponge, the high-purity aluminum, the zirconium sponge, the high-purity tin, the high-purity silicon, the aluminum-molybdenum intermediate alloy, the aluminum-tungsten intermediate alloy, the aluminum-niobium intermediate alloy and the C powder which are weighed in the second step into a plurality of alloy blocks; the alloy block sequentially comprises titanium sponge, zirconium sponge, aluminum-niobium intermediate alloy, C powder, aluminum-molybdenum intermediate alloy, aluminum-tungsten intermediate alloy, high-purity tin, high-purity silicon and high-purity aluminum from bottom to top; wherein the powder C is wrapped by aluminum foil;
fourthly, B weighed in the second step4Wrapping the powder C by using aluminum foil, and pressing into a plurality of secondary feeding blocks;
fifthly, preheating: preheating the steel die, the alloy block prepared in the third step and the secondary feeding block prepared in the fourth step;
sixthly, smelting:
cleaning the interior of a water-cooled copper crucible and a secondary charging hopper;
uniformly spreading granular titanium sponge at the bottom of the water-cooled copper crucible; vertically placing a titanium rod in the middle of a water-cooled copper crucible, uniformly placing the alloy blocks processed in the fifth step around the titanium rod, placing the secondary feeding block into a secondary feeding hopper, and closing a furnace door of the vacuum induction smelting furnace;
starting a vacuum pump to vacuumize the vacuum induction melting furnace until the pressure reaches below 5Pa, and filling argon until the internal pressure is 80% -90% of the external pressure; opening a water cooling machine;
fourthly, repeating the step III for 1-3 times, and filling argon into the furnace;
starting a power supply, loading the power to 30-40 kW, and keeping for 5-10 min; then, loading power at the speed of 5kW/min to 7.5kW/min until the power is 60kW to 70kW, keeping for 5min to 10min, and completely melting the materials in the furnace;
sixthly, adding the secondary feeding block to the middle of the crucible through a secondary feeding hopper, loading power at the speed of 10-20 kW/min until the power is 75-90 kW, stirring at a high speed of 800-1000 rpm for 3-5 min, and then stirring at a low speed of 300-500 rpm for 5-10 min to obtain a refined alloy melt;
seventhly, overturning the water-cooled copper crucible by 160 degrees, pouring the alloy melt into a steel mold, turning off an induction melting power supply, cooling in the furnace for 30-40 min, introducing argon, opening a furnace door, and taking out an alloy ingot in the steel mold;
seventhly, heat treatment: and carrying out homogenizing annealing treatment on the alloy ingot obtained in the sixth step at 650-700 ℃ to obtain the multi-element reinforced high-temperature titanium-based composite material.
2. The method of claim 1, wherein in the second step, the mass content of Mo in the Al-Mo intermediate alloy is 50.5%, the mass content of W in the Al-W intermediate alloy is 57.44%, and the mass content of Nb in the Al-Nb intermediate alloy is 83.15%.
3. The method of claim 1, wherein the reinforcing phase of step two is further added with nano-Y2O3Powder of Y2O3The volume percentage of the component (B) is less than or equal to 0.5.
4. The method of claim 3, wherein the reinforcing phase is added with nano-Y2O3When the powder is prepared, step four, weighing the B4C powder and nano-Y2O3And uniformly mixing the powder, wrapping the powder by using an aluminum foil, and pressing the powder into a plurality of secondary feeding blocks.
5. The method of claim 1, wherein the thickness of the aluminum foil in the third and fourth steps is 0.006 mm.
6. The method for preparing the multielement reinforced high temperature titanium-based composite material according to claim 1, wherein the diameter of the alloy block in the third step is 20-30 mm, and the height of the alloy block is 40-50 mm.
7. The method for preparing the multielement reinforced high temperature titanium-based composite material according to claim 1, wherein the diameter of the secondary feeding block in the fourth step is 5-10 mm, and the height thereof is 10-20 mm.
8. The method for preparing the multielement reinforced high-temperature titanium-based composite material according to claim 1, wherein the preheating temperature of the die is controlled to be 200-500 ℃ in step five, and the preheating time is 1 h.
9. The method for preparing the multielement reinforced high-temperature titanium-based composite material according to claim 1, wherein the preheating temperature of the alloy block is controlled to be 50-200 ℃ in the fifth step, and the preheating time is 1 hour.
10. The method for preparing the multielement reinforced high temperature titanium-based composite material according to claim 1, wherein the preheating temperature of the secondary feeding block is controlled to be 50-300 ℃ in the fifth step, and the preheating time is 30 min.
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