CN114393209B - Titanium-based composite powder with core-shell structure and preparation method and application thereof - Google Patents

Titanium-based composite powder with core-shell structure and preparation method and application thereof Download PDF

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CN114393209B
CN114393209B CN202210237845.7A CN202210237845A CN114393209B CN 114393209 B CN114393209 B CN 114393209B CN 202210237845 A CN202210237845 A CN 202210237845A CN 114393209 B CN114393209 B CN 114393209B
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titanium
powder
based composite
mixture
core
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CN114393209A (en
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安琦
黄陆军
王帅
张芮
王存玉
陈润
孟凡超
耿林
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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
    • 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
    • C22C32/0084—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 carbon or graphite as the main non-metallic constituent
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • 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
    • 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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Abstract

The invention relates to the technical field of titanium-based composite materials, in particular to titanium-based composite powder with a core-shell structure, and a preparation method and application thereof. The preparation method of the titanium-based composite material comprises the following steps: step one: uniformly mixing titanium metal powder and ceramic powder to obtain a mixture, wherein the particle size of the ceramic powder is smaller than that of the titanium metal powder; step two: heating the mixture to raise the temperature of the mixture to a preset temperature, wherein the preset temperature is a temperature at which in-situ autogenous reaction of titanium metal powder and ceramic occurs; step three: and carrying out heat preservation treatment on the mixture at the preset temperature to obtain the titanium-based composite powder with the core-shell structure. The invention provides a titanium-based composite powder with a core-shell structure and a preparation method thereof, and the titanium-based composite powder can be applied to the preparation of a titanium-based composite material by an additive manufacturing technology.

Description

Titanium-based composite powder with core-shell structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of titanium-based composite materials, in particular to titanium-based composite powder with a core-shell structure, and a preparation method and application thereof.
Background
The titanium-based composite material has excellent properties such as high specific strength, high temperature resistance and the like, and is an important material applied to the technical field of aerospace, such as the preparation of parts of an aircraft by adopting the titanium-based composite material. The additive manufacturing technology is a manufacturing technology for integrally forming powder raw materials and is a main technical means for preparing titanium-based composite material parts at present.
In the prior art, the method for preparing the titanium-based composite material by using the additive manufacturing technology mainly comprises the following three steps: (1) The method comprises the steps of firstly uniformly mixing titanium metal powder and fine reinforcement powder to enable ceramic powder to be distributed on the surfaces of titanium metal powder particles, then utilizing an additive manufacturing technology to manufacture a titanium-based composite material, wherein the bonding strength of the ceramic distributed on the surfaces of the titanium metal and the titanium metal is weak, and the ceramic is easy to fall off in the powder feeding process, so that the microstructure and the performance of the manufactured titanium-based composite material are affected. In addition, during additive manufacturing, ceramic powder and titanium metal powder may undergo in-situ autogenous reactions, which are exothermic reactions, causing localized thermal stress increases, thereby increasing the risk of cracking of the titanium-based composite. (2) Firstly, processing titanium metal and ceramic into a titanium-based composite material rod by using a hot-pressing sintering or fusion casting method, then processing the titanium-based composite material rod into titanium-based composite powder by using an air atomization powder process technology or a rotating electrode powder process technology, and then preparing the titanium-based composite powder into the titanium-based composite material by using an additive manufacturing technology. The titanium-based composite powder prepared by the method has high quality and good performance, and the in-situ autogenous reaction does not occur in the subsequent additive manufacturing process of the titanium-based composite material due to the in-situ autogenous reaction occurring in the process of manufacturing the titanium-based composite powder, so that the problem of thermal stress caused by the reaction is avoided. However, the preparation method has the advantages of complex process, long period and high cost. (3) And (3) respectively conveying the titanium metal powder and the ceramic powder into a molten pool by utilizing two powder conveying systems, and directly preparing the titanium-based composite material by utilizing an additive manufacturing technology. However, the method is easy to cause uneven mixing and insufficient reaction of the two powders, so that the prepared titanium-based composite material has defects inside, poor microstructure and poor performance.
Disclosure of Invention
The embodiment of the invention provides titanium-based composite powder with a core-shell structure, a preparation method and application thereof, and can provide titanium-based composite powder with a core-shell structure and a preparation method thereof.
In a first aspect, a method for preparing a core-shell structured titanium-based composite powder, comprising:
step one: uniformly mixing titanium metal powder and ceramic powder to obtain a mixture, wherein the particle size of the ceramic powder is smaller than that of the titanium metal powder;
step two: heating the mixture to raise the temperature of the mixture to a preset temperature, wherein the preset temperature is a temperature at which in-situ autogenous reaction of titanium metal powder and ceramic occurs;
step three: and carrying out heat preservation treatment on the mixture at the preset temperature to obtain the titanium-based composite powder with the core-shell structure.
Preferably, in the first step, the titanium metal powder is pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder, and the ceramic powder is graphite powder or TiB 2 Powder or B 4 And C, powder.
Preferably, in the first step, the particle size of the titanium metal powder is 50 to 200 μm, and the particle size of the ceramic powder is 0.5 to 8 μm.
Preferably, in step one, the method includes:
ball milling is carried out on the titanium metal powder and the ceramic powder for 3-6 hours in an argon atmosphere, the rotational speed of the ball milling is 150-250r/min, and the ball-to-material ratio is (2-6): 1.
Preferably, the ball milling tank and the grinding balls of the ball milling treatment are made of hard alloy.
Preferably, in the first step, after the ball milling treatment, the obtained mixture is subjected to a standing treatment in an argon atmosphere for more than 5 hours.
Preferably, in the second step, the heating treatment is performed under a vacuum atmosphere having a vacuum degree of 1×10 -3 ～1×10 -2 Pa, wherein the preset temperature is 700-1100 ℃.
Preferably, in the third step, the heat-retaining treatment is performed under a vacuum atmosphere having a vacuum degree of 1×10 -3 ～1×10 -2 Pa, the treatment time of the heat preservation treatment is 0.5-2 h.
In a second aspect, the present invention provides a titanium-based composite powder having a core-shell structure, which is prepared by the preparation method according to any one of the first aspects.
Preferably, the volume fraction of the reinforcement phase in the titanium-based composite is 1 to 10vol.%.
In a third aspect, the present invention provides an application of the titanium-based composite powder with a core-shell structure, where the titanium-based composite powder is the titanium-based composite powder described in the second aspect, and the titanium-based composite powder is applied to preparing a titanium-based composite material by adopting an additive manufacturing technology.
Compared with the prior art, the invention has at least the following beneficial effects:
in the invention, titanium metal powder and ceramic powder are uniformly mixed, so that fine ceramic powder is uniformly coated on the particle surfaces of the titanium metal powder, and a mixture with a ceramic-coated titanium metal structure is obtained. And (3) heating the mixture to enable the temperature to reach a preset temperature, and enabling the ceramics and the titanium metal to perform in-situ autogenous reaction at the preset temperature, wherein titanium element on the surface of titanium metal particles starts to react with the ceramics coated on the surface of the titanium metal particles to generate a reinforcing phase. And (3) carrying out heat preservation treatment on the mixture at the preset temperature, providing sufficient reaction time for in-situ autogenous reaction of the ceramic and the titanium metal, enabling the reaction to be carried out more fully, enabling the ceramic coated on the surface of the titanium metal particle to fully react to form a reinforcing phase, and enabling the reinforcing phase to be coated on the surface of the titanium metal particle to form a core-shell structure, thereby obtaining the titanium-based composite powder with the core-shell structure.
In the invention, the reinforcing phase is directly generated on the surface of the titanium metal particles, so that the interface bonding strength of the reinforcing phase and the titanium metal particles is high, and the reinforcing phase is not easy to fall off. In addition, because the titanium-based composite powder with the core-shell structure provided by the invention has in-situ autogenous reaction during preparation, the titanium-based composite powder with the core-shell structure does not have in-situ autogenous reaction when the titanium-based composite material is prepared by adopting an additive manufacturing technology, so that the problem of local thermal stress increase during the process of manufacturing the titanium-based composite material by additive manufacturing is avoided, and the prepared titanium-based composite material has good performance and is not easy to crack.
In the invention, the titanium-based composite powder with the core-shell structure can be obtained by uniformly mixing the titanium metal powder and the ceramic powder and then carrying out heating and heat preservation treatment. In addition, the prepared titanium-based composite powder with the core-shell structure has high sphericity and good fluidity, and the variety, size and reinforcing phase content of the powder can be adjusted by adjusting the variety, particle size and mass ratio of the titanium metal powder and the ceramic powder.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a cross-sectional electron microscope of a titanium-based composite powder particle with a core-shell structure according to embodiment 2 of the present invention;
FIG. 2 is a partial enlarged view of a cross-sectional electron microscope of a titanium-based composite powder particle with a core-shell structure according to embodiment 2 of the present invention;
FIG. 3 is a surface-area electron microscope image of a titanium-based composite powder particle with a core-shell structure according to example 2 of the present invention;
fig. 4 is a partial enlarged view of a surface area electron microscope of a titanium-based composite powder particle with a core-shell structure according to embodiment 2 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The embodiment of the invention provides a preparation method of titanium-based composite powder with a core-shell structure, which comprises the following steps:
step one: uniformly mixing titanium metal powder and ceramic powder to obtain a mixture, wherein the particle size of the ceramic powder is smaller than that of the titanium metal powder;
step two: heating the mixture to raise the temperature of the mixture to a preset temperature, wherein the preset temperature is a temperature at which in-situ autogenous reaction of titanium metal powder and ceramic occurs;
step three: and carrying out heat preservation treatment on the mixture at the preset temperature to obtain the titanium-based composite powder with the core-shell structure.
In the invention, titanium metal powder and ceramic powder are uniformly mixed, so that fine ceramic powder is uniformly coated on the particle surfaces of the titanium metal powder, and a mixture with a ceramic-coated titanium metal structure is obtained. And (3) heating the mixture to enable the temperature to reach a preset temperature, and enabling the ceramics and the titanium metal to perform in-situ autogenous reaction at the preset temperature, wherein titanium element on the surface of titanium metal particles starts to react with the ceramics coated on the surface of the titanium metal particles to generate a reinforcing phase. And (3) carrying out heat preservation treatment on the mixture at the preset temperature, providing sufficient reaction time for in-situ autogenous reaction of the ceramic and the titanium metal, enabling the reaction to be carried out more fully, enabling the ceramic coated on the surface of the titanium metal particle to fully react to form a reinforcing phase, and enabling the reinforcing phase to be coated on the surface of the titanium metal particle to form a core-shell structure, thereby obtaining the titanium-based composite powder with the core-shell structure.
In the invention, the reinforcing phase is directly generated on the surface of the titanium metal particles, so that the interface bonding strength of the reinforcing phase and the titanium metal particles is high, and the reinforcing phase is not easy to fall off. In addition, because the titanium-based composite powder with the core-shell structure provided by the invention has in-situ autogenous reaction during preparation, the titanium-based composite powder with the core-shell structure does not have in-situ autogenous reaction when the titanium-based composite material is prepared by adopting an additive manufacturing technology, so that the problem of local thermal stress increase during the process of manufacturing the titanium-based composite material by additive manufacturing is avoided, and the prepared titanium-based composite material has good performance and is not easy to crack.
In the invention, the titanium-based composite powder with the core-shell structure can be obtained by uniformly mixing the titanium metal powder and the ceramic powder and then carrying out heating and heat preservation treatment. In addition, the prepared titanium-based composite powder with the core-shell structure has high sphericity and good fluidity, and the variety, size and reinforcing phase content of the powder can be adjusted by adjusting the variety, particle size and mass ratio of the titanium metal powder and the ceramic powder.
According to some preferred embodiments, in step one, the titanium metal powder is pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder, and the ceramic powder is graphite powder, tiB 2 Powder or B 4 And C, powder.
In the invention, pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder is selected to prepare titanium-based composite powder with a core-shell structure, wherein the TA15 titanium alloy has excellent high-temperature resistance; meanwhile, the type of the titanium alloy powder can be selected according to the use requirement.
In the present invention, tiB 2 After being mixed with titanium metal powder, the ceramic powder can undergo in-situ autogenous reaction at a preset temperature to form a stable TiB reinforcing phase. After being mixed with titanium metal powder, graphite powder can undergo in-situ autogenous reaction at a preset temperature to form a stable TiC reinforcing phase. B (B) 4 C ceramic powder and titanium metal powder can be mixedThe in-situ autogenous reaction can occur at a preset temperature to form stable TiC and TiB reinforcement phases.
It should be noted that the titanium metal powder is not limited to the above titanium alloy powder, and any titanium-containing alloy is suitable for the preparation method provided by the present invention.
According to some preferred embodiments, in step one, the particle size of the titanium metal powder is 50 to 200 μm (e.g., may be 50 μm, 100 μm, 150 μm or 200 μm), and the particle size of the ceramic powder is 0.5 to 8 μm (e.g., may be 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm or 8 μm).
In the invention, the particle size of the ceramic powder is 0.5-8 mu m, and the particle size of the titanium powder is 50-200 mu m, so that after the two powders are uniformly mixed, the fine ceramic powder can be wrapped on the surface of the titanium powder particles.
According to some preferred embodiments, in step one, comprising:
ball milling is carried out on the titanium metal powder and the ceramic powder for 3-6 h (for example, 3h, 4h, 5h or 6 h) in an argon atmosphere, the rotating speed of the ball milling is 150-250r/min (for example, 150r/min, 200r/min or 250 r/min), and the ball-to-material ratio is (2-6): 1 (for example, 2:1, 3:1, 4:1, 5:1 or 6:1).
In the invention, the titanium metal powder and the ceramic powder can be fully and uniformly mixed by utilizing ball milling treatment, and the argon atmosphere can protect the titanium metal powder and the ceramic powder from being oxidized in the ball milling process. In the ball milling process, under the action of the grinding balls, the ceramic powder is adhered and wrapped on the surfaces of the titanium metal powder particles.
It should be noted that in the scheme of the invention, the low-energy ball milling treatment with the rotating speed of 150-250r/min can meet the requirement of uniformity in the invention. According to some preferred embodiments, the ball milling pot and the milling balls of the ball milling process are made of cemented carbide.
In the invention, the hard alloy has a series of excellent performances such as high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, and particularly the high hardness and wear resistance of the hard alloy are suitable for manufacturing ball milling tanks and grinding balls. The ball milling treatment is carried out by adopting the ball milling tank and the grinding balls which are made of hard alloy, so that the ceramic powder can be adhered and coated on the surface of the titanium metal powder particles more uniformly.
According to some preferred embodiments, in step one, after the ball milling treatment, the resulting mixture is subjected to a rest treatment in an argon atmosphere for a time greater than 5 hours.
In the invention, the mixture powder is subjected to standing treatment in an argon atmosphere because of the high temperature of the mixture powder after ball milling treatment, so that the heat of the mixture powder is reduced to room temperature (15-35 ℃), and the mixture powder with high temperature can be prevented from being oxidized by the reaction of oxygen so as to pollute the mixture powder.
According to some preferred embodiments, in step two, the heating treatment is performed under a vacuum environment having a vacuum degree of 1×10 -3 ～1×10 -2 Pa, the preset temperature is 700 to 1100 ℃ (for example, it may be 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or 1100 ℃).
In the invention, the temperature is increased to the preset temperature in the vacuum environment, so that the ceramic and the titanium metal react, the titanium metal powder cannot be melted, and the generated reinforcing phase has small size and uniform distribution. If the temperature of the heating treatment cannot reach 700 ℃, the ceramic and the titanium metal cannot be fully reacted, and the ceramic can be remained; if the temperature of the heating treatment is higher than 1100 ℃, the titanium metal powder is seriously softened and is mutually stuck and agglomerated, and the prepared titanium-based composite material has poor powder quality and low powder rate.
According to some preferred embodiments, in step three, the incubation treatment is performed under a vacuum environment having a vacuum level of 1×10 -3 ～1×10 -2 Pa, the treatment time of the heat-retaining treatment is 0.5 to 2 hours (for example, 0.5 hours, 1 hour, 1.5 hours or 2 hours may be mentioned).
In the invention, the mixture is subjected to heat preservation treatment in a vacuum environment, so that the ceramic can completely react, and the ceramic completely generates a reinforcing phase.
The embodiment of the invention also provides titanium-based composite powder with a core-shell structure, which is prepared by adopting any one of the preparation methods.
Experiments prove that as shown in fig. 1-4, the titanium-based composite powder provided by the embodiment of the invention has a core-shell structure, and in an electron microscope image, nano-scale TiB reinforced phase whiskers can be observed to be uniformly wrapped outside titanium metal particles, wherein the transverse dimension of the TiB reinforced phase whiskers is nano-scale, the length-diameter ratio is larger, and the sphericity of the titanium-based composite powder is high.
According to some preferred embodiments, the volume fraction of the reinforcement phase in the titanium-based composite is between 1 and 10vol.%.
In the present invention, if a titanium-based composite powder is prepared using a graphite powder and a titanium metal powder, a volume fraction of the reinforcing phase can be 1 to 5vol.% (e.g., can be 1vol.%, 2vol.%, 3vol.%, 4vol.%, or 5 vol.%) of the TiC-reinforced titanium-based composite powder, wherein the mass fraction of the titanium metal powder is 99 to 99.8wt.% (e.g., can be 99wt.%, 99.1wt.%, 99.2wt.%, 99.3wt.%, 99.4wt.%, 99.5wt.%, 99.6wt.%, 99.7wt.%, or 99.8 wt.%), and the mass fraction of the graphite powder is 0.2 to 1wt.% (e.g., can be 0.2wt.%, 0.3wt.%, 0.4wt.%, 0.5wt.%, 0.6wt.%, 0.8wt.%, 0.9wt.%, or 1 wt.%).
If TiB is adopted 2 The powder and titanium metal powder produce a titanium-based composite powder, a volume fraction of reinforcing phase of 1-10 vol% (e.g., may be 1vol.%, 2vol.%, 3vol.%, 4vol.%, 5vol.%, 6vol.%, 7vol.%, 8vol.%, 9vol.%, or 10 vol.%) of TiB-reinforced titanium-based composite powder can be obtained, wherein the mass fraction of titanium metal powder is 94-99.5 wt.% (e.g., may be 94wt.%, 95wt.%, 96wt.%, 97wt.%, 98wt.%, 99wt.%, or 99.5 wt.%), tiB 2 The mass fraction of the powder is 0.5-7 wt.% (e.g., may be 0.5wt.%, 1wt.%, 2wt.%, 3wt.%, 4wt.%, 5wt.%, or 6 wt.%);
if B is adopted 4 When the titanium-based composite powder is prepared from the powder C and the titanium metal powder, the volume fraction of the reinforcing phase can be 1 to 5 vol% (for example, 1 vo)l., 2vol.%, 3vol.%, 4vol.%, or 5 vol.%) of tib+tic-reinforced titanium-based composite powder, wherein the mass fraction of titanium metal powder is 99 to 99.8wt.% (e.g., may be 99wt.%, 99.1wt.%, 99.2wt.%, 99.3wt.%, 99.4wt.%, 99.5wt.%, 99.6wt.%, 99wt.%, or 99.8 wt.%) B 4 The mass fraction of the C powder is 0.2-1 wt.% (e.g., may be 0.2wt.%, 0.3wt.%, 0.4wt.%, 0.5wt.%, 0.6wt.%, 0.7wt.%, 0.8wt.%, 0.9wt.%, or 1 wt.%).
The embodiment of the invention also provides application of the titanium-based composite powder with the core-shell structure, wherein the titanium-based composite powder is the titanium-based composite powder, and the titanium-based composite powder is applied to manufacturing of a titanium-based composite material by adopting an additive manufacturing technology.
It should be noted that additive manufacturing techniques include, but are not limited to, laser additive, electron beam additive, arc additive, and cold and hot spray.
In the invention, the titanium-based composite powder with the core-shell structure can be applied to additive manufacturing of the titanium-based composite material, so that the prepared titanium-based composite material has a compact microstructure and good mechanical properties.
In order to more clearly illustrate the technical scheme and advantages of the invention, a core-shell titanium-based composite powder and a preparation method thereof are described in detail below through several embodiments.
Example 1
100 μm of TA15 titanium alloy powder and 4 μm of TiB 2 Ball milling the powder for 5 hours in an argon atmosphere, wherein the mass fraction of the TA15 titanium alloy powder is 95wt.% and the TiB is prepared by the following steps 2 The mass fraction of the powder is 4 wt%, the rotating speed of ball milling treatment is 200r/min, the ball-material ratio is 4:1, and the mixture is obtained after standing for 6 hours in an argon atmosphere;
the mixture was subjected to vacuum of 1X 10 -3 Heating the mixture to 900 ℃;
continuing to vacuum 1×10 -3 The temperature is kept for 1h in the environment of the (2) to obtain the TiB reinforced titanium-based composite powder with a core-shell structure and a volume fraction of a reinforced phase of 6.8 vol.%.
Example 2
50 μm TC4 titanium alloy powder and 0.5 μm TiB were mixed 2 Ball milling the powder for 3 hours in an argon atmosphere, wherein the mass fraction of the TC4 titanium alloy powder is 93wt.% and TiB is obtained 2 The mass fraction of the powder is 6 wt%, the rotating speed of ball milling treatment is 150r/min, the ball-material ratio is 2:1, and the mixture is obtained after standing for 5 hours in an argon atmosphere;
the mixture was subjected to vacuum of 1X 10 -3 Heating the mixture to a temperature of 1000 ℃;
continuing to vacuum 1×10 -3 The temperature is kept for 1.5 hours, and the TiB reinforced titanium-based composite powder with the core-shell structure and the volume fraction of the reinforced phase of 10vol.% is obtained.
Example 3
200 μm of pure titanium powder and 5 μm of TiB 2 Ball milling the powder for 6 hours in an argon atmosphere, wherein the mass fraction of the pure titanium powder is 99.5wt.% and TiB is obtained 2 The mass fraction of the powder is 0.6 wt%, the rotation speed of ball milling treatment is 250r/min, the ball-material ratio is 6:1, and the mixture is obtained after standing for 6 hours in an argon atmosphere;
the mixture was subjected to vacuum of 1X 10 -2 Heating the mixture to a temperature of 800 ℃;
continuing to vacuum 1×10 -2 The temperature is kept for 0.5h, and the TiB reinforced titanium-based composite powder with the core-shell structure and the volume fraction of the reinforced phase of 1vol.% is obtained.
Example 4
Ball milling is carried out on TA15 titanium alloy powder with the thickness of 100 mu m and graphite powder with the thickness of 3 mu m for 5 hours in an argon atmosphere, wherein the mass fraction of the TA15 titanium alloy powder is 99 wt%, the mass fraction of the graphite powder is 1 wt%, the rotational speed of ball milling is 200r/min, the ball-to-material ratio is 4:1, and a mixture is obtained after standing for 6 hours in the argon atmosphere;
the mixture was subjected to vacuum of 1X 10 -3 Heating the mixture to 900 ℃;
continuing to make the vacuum degree 1×10 -3 The temperature is kept for 1h, and TiC reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 5vol.% is obtained.
Example 5
Ball milling is carried out on TA15 titanium alloy powder with the thickness of 100 mu m and graphite powder with the thickness of 4 mu m for 5 hours in an argon atmosphere, wherein the mass fraction of the TA15 titanium alloy powder is 99.8 wt%, the mass fraction of the graphite powder is 0.2 wt%, the rotational speed of ball milling is 200r/min, the ball-to-material ratio is 4:1, and the mixture is obtained after standing for 6 hours in the argon atmosphere;
the mixture was subjected to vacuum of 1X 10 -3 Heating the mixture to a temperature of 800 ℃;
continuing to vacuum 1×10 -3 The temperature is kept for 1h, and TiC reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 1vol.% is obtained.
Example 6
100 μm of TA15 titanium alloy powder and 4 μm of B 4 Ball milling the powder C in an argon atmosphere for 5 hours, wherein the mass fraction of the TA15 titanium alloy powder is 99 wt%, and the powder B is prepared by the following steps of 4 The mass fraction of the powder C is 1 wt%, the rotation speed of ball milling treatment is 200r/min, the ball-material ratio is 4:1, and the mixture is obtained after standing for 6 hours in an argon atmosphere;
the mixture was subjected to vacuum of 1X 10 -3 Heating the mixture to a temperature of 1000 ℃;
continuing to vacuum 1×10 -3 The temperature is kept for 1h in the environment of the (2) to obtain TiB+TiC reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 5 vol.%.
Example 7
100 μm of TA15 titanium alloy powder and 4 μm of B 4 Ball milling the powder C in an argon atmosphere for 5 hours, wherein the mass fraction of the TA15 titanium alloy powder is 99.8wt.%, and B is formed by the following steps of 4 The mass fraction of the powder C is 0.2 wt%, the rotation speed of ball milling treatment is 200r/min, the ball-material ratio is 4:1, and the mixture is obtained after standing for 6 hours in an argon atmosphere;
the mixture is subjected to vacuum degreeIs 1X 10 -3 Heating the mixture to 900 ℃;
continuing to vacuum 1×10 -3 The temperature is kept for 1h in the environment of the (2) to obtain TiB+TiC reinforced titanium-based composite powder with a core-shell structure and a volume fraction of a reinforced phase of 1 vol.%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (6)

1. The preparation method of the titanium-based composite powder with the core-shell structure is characterized by comprising the following steps of:
step one: uniformly mixing spherical titanium metal powder and ceramic powder to obtain a mixture, wherein the particle size of the ceramic powder is smaller than that of the titanium metal powder;
step two: carrying out vacuum heating treatment on the mixture to enable the temperature of the mixture to rise to a preset temperature, wherein the preset temperature is a temperature for enabling titanium metal powder and ceramic to undergo in-situ autogenous reaction;
step three: performing heat preservation treatment on the mixture at the preset temperature to obtain the titanium-based composite powder with the core-shell structure;
in the first step, the titanium metal powder is pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder, and the ceramic powder is graphite powder, tiB2 powder or B 4 C, powder;
in the first step, the particle size of the titanium metal powder is 50-200 mu m, and the particle size of the ceramic powder is 0.5-8 mu m;
in the second step, the heating treatment is performed in a vacuum atmosphere having a vacuum degree of 1×10 -3 ~1×10 -2 Pa, wherein the preset temperature is 700-1100 ℃;
in the third step, the heat-insulating treatment is performed under a vacuum environment with a vacuum degree of 1×10 -3 ~1×10 -2 Pa, wherein the treatment time of the heat preservation treatment is 0.5-2 h.
2. The method according to claim 1, wherein in the first step, comprising:
ball milling is carried out on the titanium metal powder and the ceramic powder for 3-6 hours in an argon atmosphere, the rotational speed of the ball milling is 150-250r/min, and the ball-to-material ratio is (2-6): 1; the ball milling tank and the grinding balls for ball milling treatment are made of hard alloy.
3. The method according to claim 2, wherein in the first step, after the ball milling treatment, the resultant mixture is subjected to a standing treatment in an argon atmosphere for a time of more than 5 hours.
4. A titanium-based composite powder of core-shell structure, characterized in that it is prepared by the preparation method of any one of claims 1-3.
5. The titanium-based composite powder according to claim 4, wherein the volume fraction of the reinforcing phase in the titanium-based composite material is 1-10 vol.%.
6. Use of a titanium-based composite powder prepared on the basis of the preparation method according to any one of claims 1 to 3 or of a titanium-based composite powder according to claim 4, characterized in that the titanium-based composite powder is applied for the preparation of a titanium-based composite material using additive manufacturing techniques.
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