CN116219218A - TiAl-based alloy and preparation method and application thereof - Google Patents

TiAl-based alloy and preparation method and application thereof Download PDF

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CN116219218A
CN116219218A CN202211652748.0A CN202211652748A CN116219218A CN 116219218 A CN116219218 A CN 116219218A CN 202211652748 A CN202211652748 A CN 202211652748A CN 116219218 A CN116219218 A CN 116219218A
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tial
based alloy
sintering
ball milling
powder
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李明骜
周涛
胡励
时来鑫
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Chongqing University 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
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C2001/0054—Fuselage structures substantially made from particular materials
    • B64C2001/0081—Fuselage structures substantially made from particular materials from metallic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

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  • Organic Chemistry (AREA)
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  • Aviation & Aerospace Engineering (AREA)
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Abstract

The invention provides a TiAl-based alloy and a preparation method and application thereof. The TiAl-based alloy contains not less than 90% of TiAl by weight, B 4 The content of C is not higher than 10%. The invention innovatively introduces and designs a multi-element blending quasi-continuous network reinforced structure with boride and carbide in TiAl-based alloy, namely, the quasi-continuous network reinforced structure is constructed in a TiAl matrix unit interface layer by in-situ autogenous of boride and carbide, and boride is utilizedThe carbide of the compound has synergistic effect, realizes the toughening of the basal body unit interface layer while stabilizing the quasi-continuous reticular reinforcing structure, and obtains the high-performance TiAl-based alloy with the capsule structural characteristic structure through the optimized regulation and control of the multi-element blending quasi-continuous reticular reinforcing structure.

Description

TiAl-based alloy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a TiAl-based alloy and a preparation method and application thereof.
Background
The light weight of the high-performance structural material is the key for improving the performance of the aerospace engine, prolonging the service life of the aerospace engine and reducing the energy consumption and the cost, and the future sustainable development of the aerospace industry is directly determined. The TiAl-based alloy has the advantages of low density, high specific strength, excellent high-temperature oxidation resistance, creep resistance and the like, and meanwhile, the density of the TiAl-based alloy is about one half of that of the nickel-based superalloy, so that the TiAl-based alloy is a primary candidate material for replacing the nickel-based superalloy to realize the large-scale weight reduction of the aerospace engine. At present, the conventional service temperature of the nickel-based superalloy is more than 1000 ℃, but the high-temperature strength of the TiAl-based alloy at the temperature is insufficient, so that the nickel-based superalloy is difficult to completely replace to meet the performance requirement of the aerospace industry on high-temperature structural materials. Therefore, the high-temperature strength of the TiAl-based alloy is obviously improved, and the TiAl-based alloy is very important to the promotion of wide application in the aerospace field.
In order to improve the mechanical property of the TiAl-based alloy, scientific researchers at home and abroad introduce different types of second-phase reinforcements into the material, and the high-temperature ultimate strength of the material is improved by controlling the growth, distribution and volume fraction of the reinforcements. The rod-shaped and granular in-situ autogenous carbide reinforcement has good self-lubricating performance, and the dispersed carbide can coordinate plastic deformation of the TiAl-based alloy while effectively improving the strength of the alloy, but has limited capability of pinning interface sliding at high temperature. Meanwhile, the rod-shaped TiB reinforcement has higher hardness and strength, can effectively pin tissue interface sliding at high temperature, and inhibits high-temperature creep of TiAl-based alloy; however, tiB is relatively brittle, which is unfavorable for improving the plasticity of the material. Therefore, further development of a technical means capable of achieving the comprehensive mechanical properties of the TiAl-based alloy is necessary.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a TiAl-based alloy and a preparation method and application thereof. The invention innovatively introduces and designs a multi-element blending quasi-continuous network reinforced structure with boride and carbide in the TiAl-based alloy, namely, the quasi-continuous network reinforced structure is built on a TiAl matrix unit interface layer through in-situ autogenous of the boride and carbide, the toughening of the matrix unit interface layer is realized while stabilizing the quasi-continuous network reinforced structure by utilizing the synergistic effect of the carbide of the boride, and the high-performance TiAl-based alloy with the capsule structural characteristic structure is obtained through the optimized regulation and control of the multi-element blending quasi-continuous network reinforced structure.
The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a TiAl-based alloy having a TiAl content of 90% by weight or more, B 4 The content of C is not higher than 10%.
Optionally, the content of TiAl in the TiAl-based alloy is 100%.
Optionally, in the TiAl-based alloy, B 4 C content is more than 0%, and the balance is TiAl.
Preferably, in the TiAl-based alloy, the content of TiAl is 95 percent, B 4 The content of C was 5%.
In a second aspect, the present invention provides a method for preparing a TiAl-based alloy, wherein the content of TiAl in the alloy is 100%, and the method for preparing the alloy comprises: sintering the spherical TiAl prealloyed powder at a certain temperature and pressure.
Further, the sintering control process includes: the sintering process adopts the protection of protective gas, the sintering pressure is 40-60 MPa, the sintering temperature is 1150-1300 ℃, the heating rate during sintering is 5-15 ℃/min, and the sintering time is 0.5-2 h.
In a third aspect, the present invention provides a method for preparing another TiAl-based alloy in which B is 4 The content of C is more than 0 percent and less than or equal to 10 percent; the balance of TiAl, and the preparation method of the alloy comprises the following steps:
step 1, spherical TiAl prealloyed powder and B 4 C powder is prepared according to the composition of TiAl-based alloy;
step 2, mixing and ball milling the raw material powder;
and step 3, sintering the mixed ball-milled raw material powder.
Further, the grain diameter of the spherical TiAl prealloy powder is 105-125 mu m, B 4 The particle size of the powder C is less than or equal to 2 mu m.
Further, the control process of the mixed ball milling comprises the following steps: ball-material ratio of ball-milling beads to raw material powder is 2-5: 1, a step of; the ball milling process adopts protection gas for protection, the ball milling rotating speed is 100-300 rpm, and the ball milling time is 1-10 h.
Preferably, the ball milling beads are stainless steel ball milling beads with the diameter of 5-20 mm.
Further, the sintering control process includes: the sintering process adopts the protection of protective gas, the sintering pressure is 40-60 MPa, the sintering temperature is 1150-1300 ℃, the heating rate during sintering is 5-15 ℃/min, and the sintering time is 0.5-2 h.
In a fourth aspect, the present invention provides an application of the TiAl-based alloy in preparing a high temperature resistant material.
In a fifth aspect, the present invention provides a high temperature resistant material, the raw material composition comprising the TiAl-based alloy.
In a sixth aspect, the present invention provides the use of the above-described refractory material for the manufacture of an aircraft.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention introduces a reinforcing structure (shown in figures 2-6) with reinforcing bodies distributed in a quasi-continuous net shape into the TiAl-based alloy. According to the H-S theory of the composite material, the mechanical property of the discontinuous net-shaped reinforced TiAl-based alloy can reach the upper limit of a theoretical value, and when the spherical soft phase is surrounded by the hard phase to form a capsule structure, the material has the highest elastic modulus, and can furthest exert the reinforcing effect of the reinforcing body and the toughening effect of the matrix, so that the comprehensive mechanical property of the material is improved. Therefore, the invention finally obtains the uniform reinforcing structure that the in-situ autogenous reinforcing body is connected with the TiAl matrix unit in a metallurgical bonding mode and is distributed in a quasi-continuous net shape around the matrix unit through regulating and controlling the growth and distribution of the reinforcing body and the volume fraction of the reinforcing body. For the independent matrix units, the reinforcement is encapsulated around the matrix units, and is uniformly distributed around the matrix units in a quasi-continuous net structure on the whole, so that the high-temperature mechanical properties of the TiAl-based alloy are remarkably improved.
2. The invention designs and introduces a multi-element blending quasi-continuous reticular reinforced structure of boride and carbide with different types and forms in TiAl-based alloy, and the structure is characterized in that B is adopted 4 C and the TiAl matrix perform in-situ autogenous reaction, and a quasi-continuous reticular reinforced structure is constructed at a matrix unit interface layer. The rod-shaped and granular in-situ authigenic carbide reinforcement has good self-lubricating performance, and the dispersion distribution of the reinforcement can coordinate plastic deformation of materials while improving the strength of TiAl-based alloy, but the capability of pinning interface sliding at high temperature is limited. In addition, the rod-shaped TiB reinforcement has higher hardness and strength, can effectively pin the sliding of a tissue interface at high temperature, and can inhibit the high-temperature creep of TiAl-based alloy; however, tiB is relatively brittle, which is unfavorable for improving the plasticity of the material. In view of this, the present invention utilizes the synergistic effect between boride and carbide to stabilize the quasi-continuous network-like reinforcing structure while achieving toughening of the TiAl matrix unit interface layer, rather than providing a single strengthening or toughening effect, thereby achieving a simultaneous increase in yield strength and ultimate strength of the material under high temperature service conditions.
3. The invention passes through micron-sized B 4 C realizes the synchronous introduction of polybasic boride and carbide reinforcing body by the in-situ autogenous of B 4 The special crystal structure and bonding mode of C regulate and control the combination process of B and C atoms and Ti and Al atoms, effectively solve the problems of aggregation, precipitation and coarsening of boride, promote the boride and carbide to be embedded into TiAl matrix units in the form of whiskers, and improve the integrity and connectivity of the TiAl matrix units.
Drawings
FIG. 1 shows a spherical TiAl prealloyed powder prepared in example one with surface embedded with B by low energy ball milling 4 SEM contrast image of spherical TiAl prealloyed powder of C powder, wherein (a) is SEM image of spherical TiAl prealloyed powder, and (B) is prepared by low-energy ball milling, and B is embedded on the surface 4 SEM image of spherical TiAl prealloyed powder of C powder.
FIG. 2 is an SEM image of the microstructure of a TiAl-based alloy with a multi-element blended quasi-continuous network reinforcement structure prepared in example I.
FIG. 3 is an SEM image of the microstructure of a TiAl-based alloy with a multi-element blended quasi-continuous network reinforcement structure prepared in example two.
Fig. 4 is an SEM image of the microstructure of the TiAl-based alloy with the multi-element blended quasi-continuous network reinforcement structure prepared in example three.
FIG. 5 is a SEM image of a microstructure of a TiAl-based alloy with a multi-element blended quasi-continuous network reinforcement structure at 10 Xmagnification prepared in example three.
Fig. 6 is an SEM image of the microstructure of the TiAl-based alloy with the multi-element blended quasi-continuous network reinforcement structure prepared in example four.
Fig. 7 is a SEM image of the micro structure of the TiAl-based alloy prepared in example six.
Fig. 8 is a graph showing the compressive mechanical properties of TiAl-based alloys with multi-element blended quasi-continuous network reinforcement structures prepared in examples one to six at 800 ℃.
Detailed Description
In the description of the present invention, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention innovatively introduces and designs a multi-element blending quasi-continuous network reinforced structure with boride and carbide in the TiAl-based alloy, namely, the quasi-continuous network reinforced structure is built on a TiAl matrix unit interface layer through in-situ autogenous of the boride and carbide, the toughening of the matrix unit interface layer is realized while stabilizing the quasi-continuous network reinforced structure by utilizing the synergistic effect of the carbide of the boride, and the high-performance TiAl-based alloy with the capsule structural characteristic structure is obtained through the optimized regulation and control of the multi-element blending quasi-continuous network reinforced structure.
Invention B 4 The preparation method of the C-doped TiAl-based alloy comprises the following steps:
step 1, pre-compounding TiAlGold powder and B 4 C powder is prepared according to the composition of TiAl-based alloy;
step 2, mixing and ball milling the raw material powder; the control process of the mixed ball milling comprises the following steps: ball-material ratio of ball-milling beads to raw material powder is 2-5: 1, a step of; the ball milling process adopts protection gas for protection, the ball milling rotating speed is 100-300 rpm, and the ball milling time is 1-10 h; the ball milling beads are stainless steel ball milling beads with the diameter of 5-20 mm;
step 3, sintering the mixed ball-milled raw material powder, wherein the sintering control process comprises the following steps: the sintering process adopts the protection of protective gas, the sintering pressure is 40-60 MPa, the sintering temperature is 1150-1300 ℃, the heating rate during sintering is 5-15 ℃/min, and the sintering time is 0.5-2 h.
In the step 2, the ball milling time determines B 4 C is uniformly distributed, the longer the ball milling time is, B 4 The more uniform the C distribution, the more uniform the finally formed reinforcement distribution; ball milling rotation speed determines B 4 C, the adhesion effect, the ball milling rotating speed is too high, so that the spherical TiAl prealloy powder is broken, and a regular quasi-continuous net-shaped reinforcing structure is not formed; too small ball milling speed can cause B 4 C is accumulated and unevenly distributed, and aggregated massive reinforcements are formed in the in-situ autogenous reaction process, so that the formation of an ideal quasi-continuous net-shaped reinforcing structure is also not facilitated, and cracks can be formed at the aggregated massive reinforcements under a load state, so that the material is broken prematurely.
In the step 3, the sintering temperature is too high, so that the grain size in the TiAl matrix is too large, even the grain size is excessively burnt and melted, a quasi-continuous net-shaped reinforced structure cannot be formed, and the mechanical property of the material is deteriorated; too low sintering temperature can cause insufficient densification degree of the material, holes are formed at the interface, and the mechanical property of the material is deteriorated; the overlong sintering time can cause overlarge grain size in the TiAl matrix, and the mechanical property of the material is deteriorated; the sintering time is too short, the in-situ autogenous reinforcement does not have enough time to grow, whiskers are difficult to form to firmly pin TiAl matrix unit interfaces, the interface binding force is reduced, and the mechanical properties of materials are deteriorated.
The present invention will be described in further detail below with reference to the accompanying drawings and the detailed description, to assist those skilled in the art in a more complete, accurate and thorough understanding of the inventive concept and technical solution thereof, and the scope of the present invention includes, but is not limited to, the following examples, any modifications made in the details and form of the technical solution thereof without departing from the spirit and scope of the present application.
Example 1
The embodiment provides a TiAl-based alloy with a quasi-continuous net-shaped reinforcing structure, which comprises the following components in percentage by weight: 99.95% TiAl,0.05% B 4 C. The preparation method comprises the following steps.
Step 1, weighing, wherein the weight percentage of the components according to claim 1 is 99.95 percent of TiAl and 0.05 percent of B 4 C, respectively weighing spherical TiAl prealloy powder and B 4 C powder is used as a raw material;
step 2, ball milling, firstly, weighing the spherical TiAl prealloy powder and B 4 Placing the powder C into a ball milling tank, and placing stainless steel ball milling beads into the ball milling tank according to a ball-to-material ratio of 5:1; then locking the ball milling tank by a locking device, and vacuumizing the interior of the ball milling tank by a vacuum pump until the air pressure in the ball milling tank reaches 10 percent -2 Stopping vacuumizing under the pressure of MPa, and filling high-purity argon into the ball milling tank until the internal air pressure of the ball milling tank is atmospheric pressure, and stopping filling high-purity argon; finally, the ball milling tank is put into a ball mill to be locked and fixed, and the ball milling is carried out for 1h at a ball milling rotating speed of 200rpm, so that the B embedded on the surface is prepared 4 The SEM image of the spherical TiAl prealloyed powder of the C powder is shown in fig. 1 (B), and the SEM image of the spherical TiAl prealloyed powder before ball milling is also shown in fig. 1 (a), and it can be seen that the surface of the TiAl prealloyed powder before ball milling can see obvious crystal grain morphology, and the surface is bright, and through a proper low-energy ball milling process, the surface is B 4 Uniformly wrapping and embedding the powder C on the surface of the spherical TiAl prealloy powder;
and 3, sintering, namely placing the mixed powder ball-milled in the step 2 into a graphite mold, placing the mold into a hot-press sintering furnace, performing hot-press sintering under the condition of 1200 ℃/50MPa/1h, cooling to room temperature along with the furnace, opening the furnace, and taking out the mold to obtain the TiAl-based alloy with a multi-element blending quasi-continuous network reinforcing structure, wherein a microstructure SEM image is shown in figure 2, and boride and carbide reinforcing bodies with different morphologies are uniformly distributed at an interface layer of a TiAl matrix unit in a quasi-continuous network manner, and the TiAl matrix unit has good integrity and connectivity.
Further, the particle size of the spherical TiAl prealloy powder in the step 1 is 105-125 mu m, and B 4 The particle size of the powder C is less than or equal to 2 mu m.
Further, the diameter of the stainless steel ball grinding beads in the step 2 is 5mm, and the step of filling argon after vacuumizing is repeated for 3 times, so that the air in the ball grinding tank is discharged to the greatest extent.
Further, the hot press sintering in the step 3 is performed under the protection of argon atmosphere, and the temperature rising rate during sintering is 10 ℃/min.
Example two
The embodiment provides a TiAl-based alloy with a quasi-continuous net-shaped reinforcing structure, which comprises the following components in percentage by weight: 99.90% of TiAl,0.10% of B 4 C. The preparation method comprises the following steps.
Step 1, weighing, wherein the weight percentage of the components according to claim 1 is 99.9 percent of TiAl and 0.1 percent of B 4 C, respectively weighing spherical TiAl prealloy powder and B 4 C powder is used as a raw material;
step 2, ball milling, firstly, weighing the spherical TiAl prealloy powder and B 4 Placing the powder C into a ball milling tank, and placing stainless steel ball milling beads into the ball milling tank according to a ball-to-material ratio of 5:1; then locking the ball milling tank by a locking device, and vacuumizing the interior of the ball milling tank by a vacuum pump until the air pressure in the ball milling tank reaches 10 percent -2 Stopping vacuumizing under the pressure of MPa, and filling high-purity argon into the ball milling tank until the internal air pressure of the ball milling tank is atmospheric pressure, and stopping filling high-purity argon; finally, the ball milling tank is put into a ball mill to be locked and fixed, and the low-energy ball milling is carried out for 1h at the ball milling rotating speed of 200 rpm;
and 3, sintering, namely placing the mixed powder ball-milled in the step 2 into a graphite mold, placing the mold into a hot-press sintering furnace, performing hot-press sintering under the condition of 1200 ℃/50MPa/1h, cooling to room temperature along with the furnace, opening the furnace, and taking out the mold to obtain the TiAl-based alloy with the quasi-continuous network reinforced structure, wherein a microscopic structure SEM image is shown as a graph in figure 3, and the alloy can be seen to have the quasi-continuous network reinforced structure formed by the polybromide and carbide reinforcement.
Further, the particle size of the spherical TiAl prealloy powder in the step 1 is 105-125 mu m, and B 4 The particle size of the powder C is less than or equal to 2 mu m.
Further, the diameter of the stainless steel ball grinding ball in the step 2 is 5mm, and the step of filling argon after vacuumizing is repeated for 3 times, so that the air in the ball grinding tank is discharged to the greatest extent.
Further, the hot-press sintering in the step 3 is performed under the protection of argon atmosphere, and the temperature rising rate of the sintering is 10 ℃/min.
Example III
The embodiment provides a TiAl-based alloy with a quasi-continuous net-shaped reinforcing structure, which comprises the following components in percentage by weight: 99.50% TiAl,0.50% B 4 C. The preparation method comprises the following steps.
Step 1, weighing, wherein the weight percentage of the components according to claim 1 is 99.5 percent of TiAl and 0.5 percent of B 4 C, respectively weighing spherical TiAl prealloy powder and B 4 C powder is used as a raw material;
step 2, ball milling, firstly, weighing the spherical TiAl prealloy powder and B 4 Placing the powder C into a ball milling tank, and placing stainless steel ball milling beads into the ball milling tank according to a ball-to-material ratio of 5:1; then locking the ball milling tank by a locking device, and vacuumizing the interior of the ball milling tank by a vacuum pump until the air pressure in the ball milling tank reaches 10 percent -2 Stopping vacuumizing under the pressure of MPa, and filling high-purity argon into the ball milling tank until the internal air pressure of the ball milling tank is atmospheric pressure, and stopping filling high-purity argon; finally, the ball milling tank is put into a ball mill to be locked and fixed, and the low-energy ball milling is carried out for 1.5 hours at the ball milling rotating speed of 200 rpm;
and 3, sintering, namely placing the mixed powder ball-milled in the step 2 into a graphite mold, placing the mold into a hot-press sintering furnace, performing hot-press sintering under the condition of 1200 ℃/50MPa/1h, cooling to room temperature along with the furnace, opening the furnace, and taking out the mold to obtain the TiAl-based alloy with a quasi-continuous network reinforced structure, wherein the microstructure SEM images are shown as fig. 4 and 5, and the alloy has the quasi-continuous network reinforced structure, and the reinforcement in the structure is in a whisker form, namely boride and carbide are embedded into a TiAl matrix unit in the whisker form.
Further, the particle size of the spherical TiAl prealloy powder in the step 1 is 105-125 mu m, and B 4 The particle size of the powder C is less than or equal to 2 mu m.
Further, the diameter of the stainless steel ball grinding ball in the step 2 is 5mm, and the step of filling argon after vacuumizing is repeated for 3 times, so that the air in the ball grinding tank is discharged to the greatest extent.
Further, the hot press sintering in the step 3 is performed under the protection of argon atmosphere, and the temperature rising rate during sintering is 10 ℃/min.
Example IV
The embodiment provides a TiAl-based alloy with a quasi-continuous net-shaped reinforcing structure, which comprises the following components in percentage by weight: 95.00% of TiAl and 5.00% of B 4 C. The preparation method comprises the following steps.
Step 1, weighing, wherein the weight percentage of TiAl and B are 95% and 5% respectively according to the composition of claim 1 4 C, respectively weighing spherical TiAl prealloy powder and B 4 C powder is used as a raw material;
step 2, ball milling, firstly, weighing the spherical TiAl prealloy powder and B 4 Placing the powder C into a ball milling tank, and placing stainless steel ball milling beads into the ball milling tank according to a ball-to-material ratio of 5:1; then locking the ball milling tank by a locking device, and vacuumizing the interior of the ball milling tank by a vacuum pump until the air pressure in the ball milling tank reaches 10 percent -2 Stopping vacuumizing under the pressure of MPa, and filling high-purity argon into the ball milling tank until the internal air pressure of the ball milling tank is atmospheric pressure, and stopping filling high-purity argon; finally, the ball milling tank is put into a ball mill to be locked and fixed, and the low-energy ball milling is carried out for 8 hours at the ball milling rotating speed of 200 rpm;
and 3, sintering, namely placing the mixed powder ball-milled in the step 2 into a graphite mold, placing the mold into a hot-press sintering furnace, performing hot-press sintering under the condition of 1200 ℃/50MPa/1h, cooling to room temperature along with the furnace, opening the furnace, and taking out the mold to obtain the TiAl-based alloy with a quasi-continuous network reinforcing structure, wherein a microstructure SEM image is shown in figure 6, and boride and carbide reinforcing bodies with different morphologies are distributed in a quasi-continuous network form on the interface of TiAl matrix units.
Further, the particle size of the spherical TiAl prealloy powder in the step 1 is 105-125 mu m, and B 4 The particle size of the powder C is less than or equal to 2 mu m.
Further, the diameter of the stainless steel ball grinding ball in the step 2 is 5mm, and the step of filling argon after vacuumizing is repeated for 3 times, so that the air in the ball grinding tank is discharged to the greatest extent.
Further, the hot press sintering in the step 3 is performed under the protection of argon atmosphere, and the temperature rising rate during sintering is 10 ℃/min.
Example five
The embodiment provides a TiAl-based alloy with a quasi-continuous net-shaped reinforcing structure, which comprises the following components in percentage by weight: 90.00% of TiAl and 10.00% of B 4 C. The preparation method comprises the following steps.
Step 1, weighing, namely 90 percent of TiAl and 10 percent of B according to the weight percentage of the components of claim 1 4 C, respectively weighing spherical TiAl prealloy powder and B 4 C powder is used as a raw material;
step 2, ball milling, firstly, weighing the spherical TiAl prealloy powder and B 4 Placing the powder C into a ball milling tank, and placing stainless steel ball milling beads into the ball milling tank according to a ball-to-material ratio of 5:1; then locking the ball milling tank by a locking device, and vacuumizing the interior of the ball milling tank by a vacuum pump until the air pressure in the ball milling tank reaches 10 percent -2 Stopping vacuumizing under the pressure of MPa, and filling high-purity argon into the ball milling tank until the internal air pressure of the ball milling tank is atmospheric pressure, and stopping filling high-purity argon; finally, the ball milling tank is put into a ball mill to be locked and fixed, and the low-energy ball milling is carried out for 8 hours at the ball milling rotating speed of 200 rpm;
and 3, sintering, namely placing the mixed powder ball-milled in the step 2 into a graphite mold, placing the mold into a hot-press sintering furnace, performing hot-press sintering under the condition of 1200 ℃/50MPa/1h, cooling to room temperature along with the furnace, and taking out the mold after opening the furnace to obtain the TiAl-based alloy with the quasi-continuous net-shaped reinforced structure.
Further, the particle size of the spherical TiAl prealloy powder in the step 1 is 105-125 mu m, and B 4 The particle size of the powder C is less than or equal to 2 mu m.
Further, the diameter of the stainless steel ball grinding ball in the step 2 is 5mm, and the step of filling argon after vacuumizing is repeated for 3 times, so that the air in the ball grinding tank is discharged to the greatest extent.
Further, the hot press sintering in the step 3 is performed under the protection of argon atmosphere, and the temperature rising rate during sintering is 10 ℃/min.
Example six
The embodiment provides a compact TiAl-based alloy with a matrix in a binary structure, which comprises the following components in percentage by weight: 100.00% TiAl. The preparation method comprises the following steps.
Placing the weighed TiAl prealloy powder into a graphite mold, placing the mold into a hot-pressing sintering furnace, performing hot-pressing sintering under the condition of 1200 ℃/50MPa/1h, cooling to room temperature along with the furnace, and taking out the mold after opening the furnace to obtain a compact TiAl-based alloy with a matrix in a double-state structure, wherein a microstructure SEM image is shown in figure 7, and the microstructure is shown as a graph, wherein the TiAl-based alloy in a sintering state structure is compact in combination between the TiAl matrices, and the TiAl-based alloy structure is in the double-state structure, but a quasi-continuous net-shaped reinforcing structure does not exist in the structure.
Further, the particle size of the spherical TiAl prealloy powder in the step is 105-125 μm.
Further, the hot press sintering in the step is carried out under the protection of argon atmosphere, and the heating rate during sintering is 10 ℃/min
The TiAl-based alloys prepared in examples one to six were subjected to compression performance test at 800 c, the high temperature compression performance curves are shown in fig. 8, and the detailed results are shown in table 1.
TABLE 1
Figure BDA0004006548730000111
In summary, the invention has the following technical advantages:
1. the invention introduces a reinforcing structure (shown in figures 2-6) with reinforcing bodies distributed in a quasi-continuous net shape into the TiAl-based alloy. According to the H-S theory of the composite material, the mechanical property of the discontinuous net-shaped reinforced TiAl-based alloy can reach the upper limit of a theoretical value, and when the spherical soft phase is surrounded by the hard phase to form a capsule structure, the material has the highest elastic modulus, and can furthest exert the reinforcing effect of the reinforcing body and the toughening effect of the matrix, so that the comprehensive mechanical property of the material is improved. Therefore, the invention finally obtains the uniform reinforcing structure that the in-situ autogenous reinforcement body is connected with the TiAl matrix unit in a metallurgical bonding mode and is distributed in a quasi-continuous net shape around the matrix unit through controlling the growth, distribution and volume fraction of the reinforcement body. For the independent matrix units, the reinforcement is encapsulated around the matrix units, and is uniformly distributed around the matrix units in a quasi-continuous net structure on the whole, so that the high-temperature mechanical properties of the TiAl-based alloy are remarkably improved.
2. The invention designs and introduces a multi-element blending quasi-continuous reticular reinforced structure with boride and carbide of different types and forms into TiAl-based alloy, and builds the quasi-continuous reticular reinforced structure in a basal body unit interface layer through in-situ autogenous reaction of B and C elements and a TiAl basal body. The rod-shaped and granular in-situ authigenic carbide reinforcement has good self-lubricating performance, and the dispersion distribution of the reinforcement can coordinate plastic deformation of a material while improving the strength of the TiAl-based alloy, but the capability of pinning interface sliding at high temperature is limited. In addition, the rod-shaped TiB reinforcement has higher hardness and strength, can effectively pin tissue interface sliding at high temperature, and inhibits high-temperature creep of TiAl-based alloy; however, tiB is relatively brittle, which is unfavorable for improving the plasticity of the material. In view of this, the present invention utilizes the synergistic effect between boride and carbide to stabilize the quasi-continuous network reinforcing structure while achieving toughening of the matrix unit interfacial layer, rather than providing a single strengthening or toughening effect, thereby achieving simultaneous elevation of yield strength and ultimate compressive strength of the material under high temperature service conditions.
3. The invention passes through micron-sized B 4 C realizes the synchronous introduction of polybasic boride and carbide reinforcing body by the in-situ autogenous of B 4 The special crystal structure and bonding mode of C regulate and control the combination process of B and C atoms and Ti and Al atoms, effectively solve the problems of aggregation, precipitation and coarsening of boride, promote the boride and carbide to be embedded into TiAl matrix units in the form of whiskers, and improve the integrity and connectivity of the matrix units.
4. The invention realizes micron-sized B by utilizing low-energy ball milling technology under the protection of high-purity argon atmosphere 4 The C powder is uniformly embedded on the surface of the spherical TiAl prealloy powder, does not damage the surface morphology of the spherical TiAl prealloy powder, is favorable for obtaining a complete quasi-continuous net-shaped reinforcing structure, greatly avoids oxidation of raw material powder, and reduces the danger and cost in the ball milling process.
5. The invention passes through micron-sized B 4 C introduces B and C elements, and utilizes in-situ autogenous synergism of the B and C elements to introduce polybasic mixed boride and carbide. Wherein, micron-sized B 4 The introduction cost of B and C elements is effectively reduced from the raw materials, and the introduction efficiency of B and C elements is improved; b and C have good compatibility with TiAl matrix, similar expansion coefficient, firm and stable combination with the matrix, and are favorable for improving the mechanical property of the materials.
6. The invention can change the micron-sized B 4 And C, controlling the volume fraction of the reinforcement by weight percentage, controlling the distribution of the reinforcement by regulating and controlling the low-energy ball milling process parameters, controlling the types of the reinforcement by regulating and controlling the components of the spherical TiAl prealloy powder and the sintering process parameters, and finally realizing the optimal regulation and control of the multi-element blending quasi-continuous net-shaped reinforcement structure.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A TiAl-based alloy characterized by: the TiAl content in the alloy is not less than 90 percent by weight, B 4 The content of C is not higher than 10%.
2. A TiAl-based alloy according to claim 1, characterized in that: the TiAl-based alloy contains 100% of TiAl.
3. A TiAl-based alloy according to claim 1, characterized in that: in the TiAl-based alloy, B 4 C content is more than 0%, and the balance is TiAl.
4. A TiAl-based alloy according to claim 1, characterized in that: in the TiAl-based alloy, the content of TiAl is 95 percent, B 4 The content of C was 5%.
5. A preparation method of TiAl-based alloy is characterized in that: the TiAl content in the alloy is 100%, and the preparation method of the alloy comprises the following steps: sintering the spherical TiAl prealloyed powder at a certain temperature and pressure.
6. A preparation method of TiAl-based alloy is characterized in that: b in the alloy 4 The weight percentage of C is more than 0 percent and less than or equal to 10 percent; the balance of TiAl, and the preparation method of the TiAl-based alloy comprises the following steps:
step 1, spherical TiAl prealloyed powder and B 4 C powder is prepared according to the composition of TiAl-based alloy;
step 2, mixing and ball milling the raw material powder;
and step 3, sintering the mixed ball-milled raw material powder.
7. A method of producing a TiAl-based alloy according to claim 5 or 6, characterized in that: the sintering control process comprises the following steps: the sintering process adopts the protection of protective gas, the sintering pressure is 40-60 MPa, the sintering temperature is 1150-1300 ℃, the heating rate during sintering is 5-15 ℃/min, and the sintering time is 0.5-2 h.
8. Use of the TiAl-based alloy of any one of claims 1 to 4 or obtainable by the method of any one of claims 5 to 7 for the preparation of a high temperature resistant material.
9. A high temperature resistant material characterized by: the high-temperature resistant material comprises the TiAl-based alloy according to any one of claims 1 to 4 or the TiAl-based alloy obtained by the preparation method according to any one of claims 5 to 7.
10. Use of the refractory material of claim 9 for the manufacture of an aircraft.
CN202211652748.0A 2022-12-19 2022-12-19 TiAl-based alloy and preparation method and application thereof Pending CN116219218A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117802341A (en) * 2024-01-10 2024-04-02 重庆理工大学 Inner and outer double-layer coupling reinforced TiAl-based composite material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117802341A (en) * 2024-01-10 2024-04-02 重庆理工大学 Inner and outer double-layer coupling reinforced TiAl-based composite material and preparation method thereof

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