Preparation method of titanium-based material

Abstract

The invention discloses a preparation method of a titanium-based material, which comprises the following steps: ball-milling spherical titanium alloy powder with a first particle size to obtain spherical titanium alloy powder with a second particle size, the first particle size being greater than the second particle size; growing graphene on the surface of the spherical titanium alloy powder with the second granularity in situ; and the spherical titanium alloy powder with the graphene growing on the surface is sintered and subjected to hot extrusion, and the titanium-based material is obtained. The preparation method comprises the following steps: firstly preparing titanium alloy powder, then carrying out in-situ synthesis of graphene on TB9 powder to obtain TB9 titanium alloy powder coated with graphene, then adopting a spark plasma sintering technology to complete preparation of a block composite material, and preparing a graphene reinforced TB9 titanium-based composite material bar with matched strength and plasticity through a hot extrusion method.

Description

Technical Field

[0001] The invention relates to the field of preparation of titanium-based composite materials, and in particular to a method for preparing a titanium-based material. Background Art

[0002] Titanium alloys are favored by the aerospace and marine equipment fields due to their high specific strength and excellent corrosion resistance, and are gradually replacing traditional steel. However, with the increasing requirements for material strength, it is difficult to break through the existing titanium alloy strength simply through composition optimization and thermomechanical treatment. Therefore, titanium-based composite materials with added reinforcement phases have received more and more attention.

[0003] Usually, the reinforcing phase is made of ceramic material, and then the reinforcing phase and titanium powder are mixed by ball milling and other methods, and titanium-based composite materials are prepared by powder metallurgy. However, the composite materials prepared by this mechanical mixing + powder metallurgy method have poor interface bonding between the reinforcing phase and the matrix phase, resulting in a serious decrease in plasticity, and the reinforcing phase has poor dispersion, making it difficult to prepare large-scale materials. Summary of the invention

[0004] In view of this, in order to overcome at least one aspect of the above problems, an embodiment of the present invention provides a method for preparing a titanium-based material, comprising the following steps: Ball-milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size, wherein the first particle size is larger than the second particle size; in-situ growing graphene on the surface of spherical titanium alloy powder of a second particle size; The spherical titanium alloy powder with graphene grown on the surface is sintered and hot-extruded to obtain a titanium-based material.

[0005] In some embodiments, ball milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size further comprises: Putting spherical titanium alloy powder of a first particle size into a ball mill tube; The ball mill tube is placed in a liquid nitrogen chamber for ball milling to obtain spherical titanium alloy powder of the second particle size.

[0006] In some embodiments, placing the ball mill tube in a liquid nitrogen chamber for ball milling to obtain a spherical titanium alloy powder of a second particle size further comprises: The spherical titanium alloy powder of the first particle size is subjected to high-energy ball milling with figure-eight oscillation at a speed of 800-1200 rpm for 10-20 minutes to obtain the spherical titanium alloy powder of the second particle size.

[0007] In some embodiments, the spherical titanium alloy powder of the first particle size is spherical titanium alloy powder of 200-500 μm; The spherical titanium alloy powder with the second particle size is spherical titanium alloy powder with a particle size of 5 to 10 μm.

[0008] In some embodiments, in-situ growing graphene on the surface of the spherical titanium alloy powder of the second particle size further comprises: placing the spherical titanium alloy powder of the second particle size into a vacuum tube; Argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, methane is introduced, and the introduction of hydrogen and methane is stopped after the temperature is maintained for 15-18 minutes; After the temperature reached room temperature, the argon flow was stopped.

[0009] In some embodiments, argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Argon gas was introduced at a flow rate of 295-305 sccm, and hydrogen gas was introduced at a flow rate of 100-110 sccm.

[0010] In some embodiments, argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Methane was introduced at a flow rate of 25-30 sccm.

[0011] In some embodiments, spherical titanium alloy powder with graphene grown on the surface is sintered and hot-extruded to obtain a titanium-based material, further comprising: The spherical titanium alloy powder with graphene grown on the surface is subjected to spark plasma sintering at 900-1000°C and 90-100 MPa pressure for 5-10 minutes.

[0012] In some embodiments, it also includes: Hot extrusion is carried out at 880~900℃.

[0013] Based on the same inventive concept, according to another aspect of the present invention, an embodiment of the present invention further provides a titanium-based material, and the titanium-based material is prepared by the method described in any one of the above embodiments.

[0014] The present invention has one of the following beneficial technical effects: the present invention first prepares titanium alloy powder, then in-situ self-generates graphene on the TB9 powder to obtain TB9 titanium alloy powder coated with graphene, then uses spark plasma sintering technology to complete the preparation of bulk composite materials, and prepares graphene-reinforced TB9 titanium-based composite rods with matching strength and plasticity through hot extrusion. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0016] Figure 1 A schematic flow chart of a method for preparing a titanium-based material provided in an embodiment of the present invention. DETAILED DESCRIPTION

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

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

[0019] According to one aspect of the present invention, an embodiment of the present invention provides a method for preparing a titanium-based material, such as Figure 1 As shown, it may include the steps of: S1. ball-milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size, wherein the first particle size is larger than the second particle size; S2, in-situ growing graphene on the surface of spherical titanium alloy powder of the second particle size; S3. Sintering and hot-extrude the spherical titanium alloy powder with graphene grown on the surface to obtain a titanium-based material.

[0020] The present invention first prepares titanium alloy powder, and then in-situ self-generates graphene on the TB9 powder to obtain TB9 titanium alloy powder coated with graphene. Thereafter, spark plasma sintering technology is used to complete the preparation of bulk composite materials, and hot extrusion is used to prepare graphene-reinforced TB9 titanium-based composite rods with matched strength and plasticity.

[0021] In some embodiments, ball milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size further comprises: Putting spherical titanium alloy powder of a first particle size into a ball mill tube; The ball mill tube is placed in a liquid nitrogen chamber for ball milling to obtain spherical titanium alloy powder of the second particle size.

[0022] In some embodiments, placing the ball mill tube in a liquid nitrogen chamber for ball milling to obtain a spherical titanium alloy powder of a second particle size further comprises: The spherical titanium alloy powder of the first particle size is subjected to high-energy ball milling with figure-eight oscillation at a speed of 800-1200 rpm for 10-20 minutes to obtain the spherical titanium alloy powder of the second particle size.

[0023] In some embodiments, the spherical titanium alloy powder of the first particle size is spherical titanium alloy powder of 200-500 μm; The spherical titanium alloy powder with the second particle size is spherical titanium alloy powder with a particle size of 5 to 10 μm.

[0024] In some embodiments, in-situ growing graphene on the surface of the spherical titanium alloy powder of the second particle size further comprises: placing the spherical titanium alloy powder of the second particle size into a vacuum tube; Argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, methane is introduced, and the introduction of hydrogen and methane is stopped after the temperature is maintained for 15-18 minutes; After the temperature reached room temperature, the argon flow was stopped.

[0025] In some embodiments, argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Argon gas was introduced at a flow rate of 295-305 sccm, and hydrogen gas was introduced at a flow rate of 100-110 sccm.

[0026] In some embodiments, argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Methane was introduced at a flow rate of 25-30 sccm.

[0027] In some embodiments, spherical titanium alloy powder with graphene grown on the surface is sintered and hot-extruded to obtain a titanium-based material, further comprising: The spherical titanium alloy powder with graphene grown on the surface is subjected to spark plasma sintering at 900-1000°C and 90-100 MPa pressure for 5-10 minutes.

[0028] In some embodiments, it also includes: Hot extrusion is carried out at 880~900℃.

[0029] Specifically, TB9 titanium alloy spherical powder with a particle size of 200-500 μm is placed in an alumina ball mill tube, the ball mill tank is placed in a liquid nitrogen chamber, and eight-shaped oscillation high-energy ball milling is performed at a speed of 800-1200 rpm for 10-20 minutes to obtain TB9 titanium alloy powder with a particle size of 5-10 μm.

[0030] Next, TB9 titanium alloy spherical powder with a particle size of 5-10 μm was placed in the constant temperature of the CVD tube furnace. After vacuuming and removing the residual air in the tube, high-purity argon and hydrogen were introduced at a flow rate of 295-305 sccm and 100-110 sccm, respectively. The tube furnace was heated to 680-700°C in this atmosphere and kept warm for 25-30 minutes, and then methane gas was introduced with a flow rate controlled at 25-30 sccm. This state was maintained for 15-18 minutes, and the hydrogen and methane inlet valves were closed. After the sample was cooled to room temperature, the argon inlet valve was closed, the furnace door was opened, and the sample was taken out to obtain graphene-coated TB9 powder.

[0031] The obtained powder was then placed in a graphite mold with an outer diameter of 300 mm and an inner diameter of 30 mm, and sintered in a spark plasma sintering furnace at 900-1000°C and 90-100 MPa for 5-10 minutes to prepare a dense graphene-reinforced TB9 titanium-based composite material. Finally, the bulk material was hot extruded into Φ10 mm rods at 880-900°C.

[0032] Embodiment 1: The spherical powder of TB9 titanium alloy with a particle size of 200 μm was placed in an alumina ball mill tube, and the ball mill was placed in a liquid nitrogen chamber. The ball mill was subjected to high-energy ball milling with an eight-shaped oscillation at a speed of 800 rpm for 10 minutes to obtain a TB9 titanium alloy powder with a particle size of 5 μm. The spherical powder of TB9 titanium alloy with a particle size of 5 μm was placed in a constant temperature position of a CVD tube furnace. After vacuuming and removing the residual air in the tube, high-purity argon and hydrogen were introduced at a flow rate of 295 sccm and 100 sccm, respectively. The tube furnace was heated to 680 ° C and kept warm for 25 minutes under this atmosphere, and then methane gas was introduced with a flow rate controlled at 25 sccm. This state was maintained for 15 minutes, and the hydrogen and methane inlet valves were closed. After the sample was cooled to room temperature, the argon inlet valve was closed, the furnace door was opened, and the sample was taken out to obtain graphene-coated TB9 powder.

[0033] The obtained powder was then placed in a graphite mold with an outer diameter of 300 mm and an inner diameter of 30 mm, and sintered in a spark plasma sintering furnace at 900°C and 90 MPa for 5 minutes to prepare a dense graphene-enhanced TB9 titanium-based composite material. Finally, the bulk material was hot extruded into a Φ10 mm rod at 880°C. After solution aging, the tensile strength and elongation of the graphene-enhanced TB9 titanium-based composite material can reach 1655 MPa and 8.7%, respectively.

[0034] Embodiment 2: The TB9 titanium alloy spherical powder with a particle size of 300 μm was placed in an alumina ball mill tube, and the ball mill was placed in a liquid nitrogen chamber. The ball mill was subjected to high-energy ball milling with an eight-shaped oscillation at a speed of 1000 rpm for 17 minutes to obtain a TB9 titanium alloy powder with a particle size of 8 μm. The TB9 titanium alloy spherical powder with a particle size of 8 μm was placed in a constant temperature position of a CVD tube furnace. After vacuuming and removing the residual air in the tube, high-purity argon and hydrogen were introduced at a flow rate of 300 sccm and 105 sccm, respectively. The tube furnace was heated to 600 ° C and kept warm for 28 minutes under this atmosphere, and then methane gas was introduced with a flow rate controlled at 28 sccm. This state was maintained for 17 minutes, and the hydrogen and methane inlet valves were closed. After the sample was cooled to room temperature, the argon inlet valve was closed, the furnace door was opened, and the sample was taken out to obtain graphene-coated TB9 powder. The final graphene-reinforced TB9 titanium-based composite material prepared, after solution aging, has a tensile strength and elongation of 1670MPa and 9.1% respectively.

[0035] The obtained powder was then placed in a graphite mold with an outer diameter of 300 mm and an inner diameter of 30 mm, and sintered in a spark plasma sintering furnace at 960°C and 94 MPa for 8 minutes to prepare a dense graphene-reinforced TB9 titanium-based composite material. Finally, the bulk material was hot extruded at 890°C into Φ10 mm rods.

[0036] Embodiment 3: The spherical powder of TB9 titanium alloy with a particle size of 500 μm was placed in an alumina ball mill tube, and the ball mill was placed in a liquid nitrogen chamber. The ball mill was subjected to high-energy ball milling with an eight-shaped oscillation at a speed of 1200 rpm for 20 minutes to obtain a TB9 titanium alloy powder with a particle size of 5 μm. The spherical powder of TB9 titanium alloy with a particle size of 5 μm was placed in a constant temperature position of a CVD tube furnace. After vacuuming and removing the residual air in the tube, high-purity argon and hydrogen were introduced at a flow rate of 305 sccm and 110 sccm, respectively. The tube furnace was heated to 700 ° C and kept warm for 30 minutes under this atmosphere, and then methane gas was introduced with a flow rate controlled at 30 sccm. This state was maintained for 18 minutes, and the hydrogen and methane inlet valves were closed. After the sample was cooled to room temperature, the argon inlet valve was closed, the furnace door was opened, and the sample was taken out to obtain graphene-coated TB9 powder. The obtained powder was then placed in a graphite mold with an outer diameter of 300 mm and an inner diameter of 30 mm, and sintered in a spark plasma sintering furnace at 1000°C and 100 MPa for 10 minutes to prepare a dense graphene-enhanced TB9 titanium-based composite material. Finally, the bulk material was hot extruded into a Φ10 mm rod at 900°C. After solution aging, the tensile strength and elongation of the graphene-enhanced TB9 titanium-based composite material can reach 1697 MPa and 9.3%, respectively.

[0037] The scheme proposed by the present invention utilizes high-energy ball milling to ball mill TB9 titanium alloy spherical powder with a particle size of 200-500 μm at low temperature, which can effectively reduce the cold welding effect of titanium alloy powder during ball milling, making the powder more dispersed and the particle size more uniform. At the same time, the vapor deposition method is used to self-generate graphene on the surface of TB9 titanium alloy nanopowder in situ to obtain graphene-coated TB9 titanium alloy powder. After spark plasma sintering, a highly dispersed graphene-enhanced phase can be obtained. In addition, the TB9 powder is first refined, and then graphene is produced in situ on the surface of TB9 powder with a particle size of less than 10 μm. The graphene is closely bonded to the matrix phase interface, which is conducive to maintaining high plasticity while improving the strength of the material. The graphene-enhanced TB9 titanium-based composite material finally prepared can reach 1655-1697 MPa and 8.7-9.3% in tensile strength and elongation respectively after solution aging.

[0038] Based on the same inventive concept, according to another aspect of the present invention, an embodiment of the present invention further provides a titanium-based material, wherein the titanium-based material is prepared by the following steps: Ball-milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size, wherein the first particle size is larger than the second particle size; in-situ growing graphene on the surface of spherical titanium alloy powder of a second particle size; The spherical titanium alloy powder with graphene grown on the surface is sintered and hot-extruded to obtain a titanium-based material.

[0039] In some embodiments, ball milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size further comprises: Putting spherical titanium alloy powder of a first particle size into a ball mill tube; The ball mill tube is placed in a liquid nitrogen chamber for ball milling to obtain spherical titanium alloy powder of the second particle size.

[0040] In some embodiments, placing the ball mill tube in a liquid nitrogen chamber for ball milling to obtain a spherical titanium alloy powder of a second particle size further comprises: The spherical titanium alloy powder of the first particle size is subjected to high-energy ball milling with figure-eight oscillation at a speed of 800-1200 rpm for 10-20 minutes to obtain the spherical titanium alloy powder of the second particle size.

[0041] In some embodiments, the spherical titanium alloy powder of the first particle size is spherical titanium alloy powder of 200-500 μm; The spherical titanium alloy powder with the second particle size is spherical titanium alloy powder with a particle size of 5 to 10 μm.

[0042] In some embodiments, in-situ growing graphene on the surface of the spherical titanium alloy powder of the second particle size further comprises: placing the spherical titanium alloy powder of the second particle size into a vacuum tube; Argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, methane is introduced, and the introduction of hydrogen and methane is stopped after the temperature is maintained for 15-18 minutes; After the temperature reached room temperature, the argon flow was stopped.

[0043] In some embodiments, argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Argon gas was introduced at a flow rate of 295-305 sccm, and hydrogen gas was introduced at a flow rate of 100-110 sccm.

[0044] In some embodiments, argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Methane was introduced at a flow rate of 25-30 sccm.

[0045] In some embodiments, spherical titanium alloy powder with graphene grown on the surface is sintered and hot-extruded to obtain a titanium-based material, further comprising: The spherical titanium alloy powder with graphene grown on the surface is subjected to spark plasma sintering at 900-1000°C and 90-100 MPa pressure for 5-10 minutes.

[0046] In some embodiments, it also includes: Hot extrusion is carried out at 880~900℃.

[0047] The above are exemplary embodiments disclosed in the present invention, but it should be noted that various changes and modifications may be made without departing from the scope disclosed in the embodiments of the present invention as defined in the claims. The functions, steps and / or actions of the method claims according to the disclosed embodiments described herein do not need to be performed in any particular order. In addition, although the elements disclosed in the embodiments of the present invention may be described or required in individual form, they may also be understood as multiple unless explicitly limited to the singular.

[0048] It should be understood that, as used herein, the singular forms "a", "an" are intended to include the plural forms as well, unless the context clearly supports an exception. It should also be understood that, as used herein, "and / or" refers to any and all possible combinations including one or more of the associated listed items.

[0049] The serial numbers of the embodiments disclosed in the above embodiments of the present invention are only for description and do not represent the advantages or disadvantages of the embodiments.

[0050] A person skilled in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other changes in different aspects of the above embodiments of the present invention, which are not provided in detail for the sake of simplicity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention should be included in the protection scope of the embodiments of the present invention.

Claims

1. A method for preparing a titanium-based material, characterized in that: The following steps are involved: Ball-milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size, wherein the first particle size is larger than the second particle size; in-situ growing graphene on the surface of spherical titanium alloy powder of a second particle size; The spherical titanium alloy powder with graphene grown on the surface is sintered and hot-extruded to obtain a titanium-based material.

2. The method according to claim 1, characterized in that The method further comprises: ball-milling a spherical titanium alloy powder of a first particle size to obtain a spherical titanium alloy powder of a second particle size. Putting spherical titanium alloy powder of a first particle size into a ball mill tube; The ball mill tube is placed in a liquid nitrogen chamber for ball milling to obtain spherical titanium alloy powder of the second particle size.

3. The method according to claim 2, characterized in that The ball mill tube is placed in a liquid nitrogen chamber for ball milling to obtain a spherical titanium alloy powder of a second particle size, further comprising: The spherical titanium alloy powder of the first particle size is subjected to high-energy ball milling with figure-eight oscillation at a speed of 800-1200 rpm for 10-20 minutes to obtain the spherical titanium alloy powder of the second particle size.

4. The method according to claim 3, characterized in that The spherical titanium alloy powder of the first particle size is spherical titanium alloy powder of 200-500 μm; The spherical titanium alloy powder with the second particle size is spherical titanium alloy powder with a particle size of 5 to 10 μm.

5. The method according to claim 1, characterized in that In-situ growing graphene on the surface of spherical titanium alloy powder of a second particle size further comprises: placing the spherical titanium alloy powder of the second particle size into a vacuum tube; Argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, methane is introduced, and the introduction of hydrogen and methane is stopped after the temperature is maintained for 15-18 minutes; After the temperature reached room temperature, the argon flow was stopped.

6. The method according to claim 5, characterized in that Argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Argon gas was introduced at a flow rate of 295-305 sccm, and hydrogen gas was introduced at a flow rate of 100-110 sccm.

7. The method according to claim 5, characterized in that Argon and hydrogen are introduced into the vacuum tube, the temperature is raised to 680-700° C. and kept at this temperature for 25-30 minutes, and then methane is introduced, further comprising: Methane was introduced at a flow rate of 25-30 sccm.

8. The method according to claim 1, characterized in that Sintering and hot extruding spherical titanium alloy powder with graphene grown on the surface to obtain a titanium-based material, further comprising: The spherical titanium alloy powder with graphene grown on the surface is subjected to spark plasma sintering at 900-1000°C and 90-100 MPa pressure for 5-10 minutes.

9. The method according to claim 8, characterized in that Also includes: Hot extrusion is carried out at 880~900℃.

10. A titanium-based material, characterized in that: The titanium-based material is prepared based on the method according to any one of claims 1 to 9.

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