High-thermal-conductivity layered titanium-based composite material with continuous graphene structure and preparation method of high-thermal-conductivity layered titanium-based composite material

Abstract

The invention relates to a high-thermal-conductivity layered titanium-based composite material with a continuous graphene structure and a preparation method of the high-thermal-conductivity layered titanium-based composite material, and belongs to the technical field of preparation of novel aerospace titanium alloy materials. In order to solve the problems that a titanium-based composite material is large in interface thermal resistance and poor in thermal conductivity, the invention provides a preparation method of a high-thermal-conductivity layered titanium-based composite material with a continuous graphene structure, and the preparation method comprises the following steps: ablating graphene paper through laser marking to form a through hole array; a titanium powder layer and graphene paper with a through hole array are laid in a mold in an overlapped mode, a layered blank for powder metallurgy is obtained, and the high-thermal-conductivity layered titanium-based composite material with the continuous graphene structure is obtained through vacuum hot pressing sintering. According to the titanium-based composite material and the preparation method thereof, a high-heat-conduction channel which is efficiently communicated is constructed, meanwhile, effective communication of the titanium matrix is guaranteed, on the premise that the low graphene content is kept, the heat conduction capacity of the titanium-based composite material is remarkably improved, and the problems of heat accumulation and local failure encountered in the part service process are effectively solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of novel aerospace titanium alloy materials, and in particular relates to a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a preparation method thereof. Background Art

[0002] With the booming aerospace industry and continuous technological innovation, the performance requirements for materials used in hot-end components of aircraft surfaces are becoming increasingly stringent, particularly in the pursuit of lightweight, heat resistance, and high strength. Titanium alloys, with their superior specific strength and modulus, excellent corrosion resistance, and exceptional high-temperature resistance, have become a key material in aerospace manufacturing. However, despite their many advantages, titanium alloys face a critical bottleneck in their application in hot-end components of aerospace surfaces, such as aircraft air fins. During service, these components generate significant amounts of aerodynamic heat due to intense friction with high-speed airflow. Titanium alloys have a relatively low intrinsic thermal conductivity of only approximately 7 W / (m·K), meaning that heat rapidly accumulated on the component surface is difficult to dissipate quickly through thermal conduction. As local temperatures rise sharply, the performance of titanium alloys degrades significantly, and softening failure may even occur, seriously impacting the stability and safety of the aircraft.

[0003] The diverse lattice vibration modes of titanium metal itself cause phonons to be severely scattered during transmission. At the same time, the low concentration of free electrons outside the nucleus of titanium atoms also affects its electronic thermal conductivity. In order to improve the thermal conductivity of titanium-based composites, it is necessary to introduce a reinforcing phase with high thermal conductivity, such as diamond, graphene and other materials. Chen et al. used directed energy deposition to prepare Ti64-based composites with a diamond content of more than 20wt.%, and their room temperature thermal conductivity increased by about 200%. However, as the diamond content increases, the composite material has the problem of inversion of strength and thermal conductivity. When the reinforcing phase content exceeds 40wt.%, more defects will be generated inside the composite material, which will not only cause a decrease in thermal conductivity, but also damage the mechanical properties of the composite material.

[0004] Yan et al. added a large amount of graphene to a titanium-based composite prepared by hot isostatic pressing, significantly improving the thermal conductivity of the titanium-based composite. However, the large amount of graphene introduced a large number of defects, making the composite exhibit significant room-temperature brittleness. Yang et al. prepared a titanium-based composite with a low graphene content by ball milling and microwave sintering. However, due to the discontinuous distribution of graphene in the titanium-based composite and severe interfacial reaction with titanium, the thermal conductivity of the titanium-based composite decreased slightly.

[0005] At present, the reinforcement phases in titanium-based composite materials with high content of reinforcement phases designed based on the theory of thermal conductivity percolation are usually disorderly distributed in the matrix, which leads to low thermal conductivity efficiency of the reinforcement phase and poor matrix connectivity. At the same time, the large number of interfaces brought about by the disordered distribution of the reinforcement phase will significantly increase the thermal resistance of the composite material. Therefore, the thermal conductivity increase of existing titanium-based composite materials is limited, and they basically have no tensile plasticity. In addition, the thermal conductivity of high thermal conductivity second phases such as graphene, carbon nanotubes and boron nitride nanosheets is directional, and the current titanium-based composite material preparation technology makes it difficult to achieve directional distribution of high thermal conductivity second phases, which also reduces the thermal conductivity efficiency of the composite material. Summary of the Invention

[0006] In order to solve the problems of large interface thermal resistance and poor thermal conductivity of titanium-based composite materials, the present invention provides a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a preparation method thereof.

[0007] The technical solution of the present invention:

[0008] A method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure, comprising the following steps:

[0009] Step 1: forming a through-hole array on the graphene paper by laser marking;

[0010] Step 2: Laying titanium powder layers and the graphene paper with through-hole arrays obtained in step 1 in an overlapping manner in a mold, with each group of layers being a layer, and laying 20 to 30 layers in total to obtain a layered blank for powder metallurgy;

[0011] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2 to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure.

[0012] Furthermore, the through-hole array in step 1 is an array of multiple through-hole structures arranged at a fixed interval, the diameter of the through-holes is 25-250 μm, and the distance between two adjacent through-holes is 0.25-1 mm.

[0013] Furthermore, the thickness of the graphene paper in step 1 is 10-100 μm.

[0014] Furthermore, the power of the laser marking in step 1 is 10-100W, the scanning speed is 30-500mm / s, and the number of scanning times is 1-3 times.

[0015] Furthermore, the thickness of the single layer of the titanium powder layer in step 2 is 200-1000 μm.

[0016] Furthermore, the titanium powder layer in step 2 is made of pure titanium powder or titanium alloy powder; the particle size of the pure titanium powder or titanium alloy powder is 15-53 μm.

[0017] Furthermore, the titanium alloy powder is TC4 titanium alloy powder, TA15 titanium alloy powder or Ti60 titanium alloy powder.

[0018] Furthermore, the vacuum degree of the vacuum hot pressing sintering in step 3 is not higher than 10 -2 Pa, sintering temperature is 900~1300℃, pressure is 50MPa, and holding time is 1h.

[0019] Furthermore, the thickness of the layered titanium-based composite material obtained in step three is 2 to 50 mm.

[0020] The invention provides a high thermal conductivity layered titanium-based composite material with a continuous graphene structure, wherein the content of the graphene is 0.5-10 wt.%.

[0021] Beneficial effects of the present invention:

[0022] The present invention is based on the theory of thermal conductivity network. It utilizes high thermal conductivity graphene paper with directional arranged graphene sheets to construct a highly interconnected high thermal conductivity channel in the titanium-based composite material through a layered configuration design. At the same time, the through-hole array on the graphene paper ensures the effective connectivity of the titanium matrix, realizes the integration of high performance and structural function, significantly enhances the thermal conductivity of titanium alloys, effectively solves the problem of heat accumulation encountered by components during service, and greatly expands the application range of titanium alloys.

[0023] The present invention uses graphene paper with a layer thickness of 20μm and 50μm to prepare 20-layer pure titanium-based layered titanium-based composite materials with a graphene content of 1.6wt.% and 4wt.%, respectively. After testing, the thermal conductivity of the layered titanium-based composite materials reached 87.9 W / (m·K) and 139.0 W / (m·K), respectively, which is 303% and 538% higher than that of the pure titanium matrix. While maintaining a low graphene content, the present invention achieves a significant improvement in the thermal conductivity of the layered titanium-based composite materials, breaking through the limitations of the thermal conductivity of titanium-based composite materials. At the same time, the titanium-based composite materials prepared with 20μm thick graphene paper still maintain a tensile plasticity of nearly 5% at room temperature, demonstrating good comprehensive performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a side view of a layered blank obtained by overlapping titanium powder layers and graphene paper with a through-hole array according to the present invention;

[0025] Figure 2 A micrograph of the longitudinal cross-section microstructure of the layered titanium-based composite material prepared in Example 1;

[0026] Figure 3A micrograph of the longitudinal cross-section microstructure of the layered titanium-based composite material prepared in Example 2;

[0027] Figure 4 The figure is a comparison diagram of room temperature tensile stress-strain curves of pure titanium, and the layered titanium-based composite materials prepared in Example 1 and Example 2. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below with reference to the embodiments, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be included in the scope of protection of the present invention. The process equipment or devices not specifically noted in the following examples are all conventional equipment or devices in the art. Unless otherwise specified, the raw materials used in the examples of the present invention can be obtained commercially; unless otherwise specified, the technical means used in the examples of the present invention are all conventional means well known to those skilled in the art.

[0029] Example 1

[0030] This embodiment provides a high thermal conductivity layered titanium-based composite material having a continuous graphene structure and a preparation method thereof.

[0031] The steps for preparing the layered titanium-based composite material of this embodiment are as follows:

[0032] Step 1: First, cut a 20μm thick graphene paper to the appropriate size. Laser marking technology was used to ablate a through-hole array on the graphene paper. The laser marking power was 50W, the scanning speed was 200mm / s, and the number of scans was 2. The through-hole array consisted of multiple through-hole structures arranged at a fixed pitch. The diameter of the through-holes was 0.25mm, and the distance between two adjacent through-holes was 1mm.

[0033] The through holes ablated on the graphene paper are used to enable the pure titanium matrix on both sides of the graphene paper to be interconnected during the subsequent preparation of the composite material, thereby improving the connectivity of the titanium matrix in the composite material.

[0034] Step 2: Lay a layer of pure titanium powder with a particle size of 15-53 μm in the mold to a thickness of 500 μm. Lay a piece of graphene paper with a through-hole array obtained in step 1 on the pure titanium powder layer. Continue to overlap the titanium powder layer and the graphene paper with a through-hole array obtained in step 1. Each group of laying is a layer, and a total of 20 layers are laid to obtain a layered blank for powder metallurgy. The side schematic diagram of the layered blank obtained by overlapping laying is shown as follows: Figure 1 shown.

[0035] In this embodiment, pure titanium powder with a diameter of 15 to 53 μm is selected so that the titanium powder can be effectively filled into the gaps in the laser-marked graphene paper, thereby achieving interconnection between the titanium powder layers above and below the graphene paper and improving the connectivity of the substrate.

[0036] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2, with the vacuum degree of vacuum hot pressing not higher than 10 -2 Pa, sintering temperature of 900 ° C, pressure of 50 MPa, and holding time of 1 h to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a thickness of 7 mm.

[0037] The longitudinal section microstructure of the layered titanium-based composite material of this embodiment is as follows: Figure 2 As shown in the figure, it can be seen that the titanium powder layers above and below the graphene paper are interconnected.

[0038] Example 2

[0039] This embodiment provides a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a preparation method thereof.

[0040] The steps for preparing the layered titanium-based composite material of this embodiment are as follows:

[0041] Step 1: First, cut a 50μm thick graphene paper to an appropriate size. Laser marking technology is used to ablate a through-hole array on the graphene paper. The through-hole array is an array of multiple through-hole structures arranged at a fixed pitch. The diameter of the through-holes is 0.25mm, and the distance between two adjacent through-holes is 1mm. In this example, the laser marking power is 100W, the scanning speed is 50mm / s, and the number of scans is 3.

[0042] Step 2: Lay a layer of pure titanium powder with a particle size of 15-53 μm in the mold to a thickness of 1000 μm, lay a piece of graphene paper with a through-hole array obtained in step 1 on the pure titanium powder layer, and continue to overlap and lay the titanium powder layer and the graphene paper with a through-hole array obtained in step 1, with each group of laying being a layer, and laying 20 layers in total to obtain a layered blank for powder metallurgy;

[0043] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2, with the vacuum degree of vacuum hot pressing not higher than 10 -2 Pa, sintering temperature of 900 ° C, pressure of 50 MPa, and holding time of 1 h to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a thickness of 7 mm.

[0044] The longitudinal section microstructure of the layered titanium-based composite material of this embodiment is as follows: Figure 3 As shown in the figure, it can be seen that the titanium powder layers above and below the graphene paper are interconnected.

[0045] Example 3

[0046] This embodiment provides a high thermal conductivity layered titanium-based composite material having a continuous graphene structure and a preparation method thereof.

[0047] The steps for preparing the layered titanium-based composite material of this embodiment are as follows:

[0048] Step 1: First, cut a 30 μm thick graphene paper to an appropriate size. Laser marking technology is used to ablate a through-hole array on the graphene paper. The through-hole array is an array of multiple through-hole structures arranged at a fixed pitch. The diameter of the through-holes is 0.05 mm, and the distance between two adjacent through-holes is 0.25 mm. In this embodiment, the laser marking power is 50 W, the scanning speed is 100 mm / s, and the number of scans is 2.

[0049] Step 2: Lay a layer of pure titanium powder with a particle size of 15-53 μm in the mold to a thickness of 330 μm, lay a piece of graphene paper with a through-hole array obtained in step 1 on the pure titanium powder layer, and continue to overlap and lay the titanium powder layer and the graphene paper with a through-hole array obtained in step 1, with each group of laying being a layer, and laying a total of 30 layers to obtain a layered blank for powder metallurgy;

[0050] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2, with the vacuum degree of vacuum hot pressing not higher than 10 -2 Pa, sintering temperature of 900 ° C, pressure of 50 MPa, and holding time of 1 h to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a thickness of 7 mm.

[0051] Example 4

[0052] This embodiment provides a high thermal conductivity layered titanium-based composite material having a continuous graphene structure and a preparation method thereof.

[0053] The steps for preparing the layered titanium-based composite material of this embodiment are as follows:

[0054] Step 1: First, cut 80 μm thick graphene paper to the appropriate size. Laser marking technology is used to ablate a through-hole array on the graphene paper. The through-hole array is an array of multiple through-hole structures arranged at a fixed pitch. The diameter of the through-holes is 0.1 mm, and the distance between two adjacent through-holes is 0.5 mm. In this example, the laser marking power is 100 W, the scanning speed is 50 mm / s, and the number of scans is 3.

[0055] Step 2: Laying a layer of TC4 titanium alloy powder with a particle size of 15-53 μm in the mold to a thickness of 1000 μm, laying a piece of graphene paper with a through-hole array obtained in step 1 on the TC4 titanium alloy powder layer, and continuing to overlap and lay the titanium powder layer and the graphene paper with a through-hole array obtained in step 1, with each group of laying being a layer, and laying a total of 25 layers to obtain a layered blank for powder metallurgy;

[0056] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2, with the vacuum degree of vacuum hot pressing not higher than 10 -2 Pa, sintering temperature of 1200 ° C, pressure of 50 MPa, and holding time of 1 h to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a thickness of 18 mm.

[0057] Example 5

[0058] This embodiment provides a high thermal conductivity layered titanium-based composite material having a continuous graphene structure and a preparation method thereof.

[0059] The steps for preparing the layered titanium-based composite material of this embodiment are as follows:

[0060] Step 1: First, cut a 10 μm thick graphene paper to an appropriate size. Laser marking technology is used to ablate a through-hole array on the graphene paper. The through-hole array is an array of multiple through-hole structures arranged at a fixed pitch. The diameter of the through-holes is 0.025 mm, and the distance between two adjacent through-holes is 0.25 mm. In this embodiment, the laser marking power is 50 W, the scanning speed is 300 mm / s, and the number of scans is 1.

[0061] Step 2: Lay a layer of TA15 titanium alloy powder with a particle size of 15-53 μm in the mold to a thickness of 200 μm, lay a piece of graphene paper with a through-hole array obtained in step 1 on the TA15 titanium alloy powder layer, and continue to overlap and lay the titanium powder layer and the graphene paper with a through-hole array obtained in step 1, with each group of laying being a layer, and laying a total of 50 layers to obtain a layered blank for powder metallurgy;

[0062] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2, with the vacuum degree of vacuum hot pressing not higher than 10 -2 Pa, sintering temperature of 1200 ° C, pressure of 50 MPa, and holding time of 1 h to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a thickness of 6 mm.

[0063] Example 6

[0064] This embodiment provides a high thermal conductivity layered titanium-based composite material having a continuous graphene structure and a preparation method thereof.

[0065] The steps for preparing the layered titanium-based composite material of this embodiment are as follows:

[0066] Step 1: First, cut a 100 μm thick graphene paper to an appropriate size. Laser marking technology is used to ablate a through-hole array on the graphene paper. The through-hole array is an array of multiple through-hole structures arranged at a fixed pitch. The diameter of the through-holes is 0.15 mm, and the distance between two adjacent through-holes is 0.4 mm. In this example, the laser marking power is 100 W, the scanning speed is 50 mm / s, and the number of scans is 5.

[0067] Step 2: Lay a layer of Ti60 titanium alloy powder with a particle size of 15-53 μm in the mold to a thickness of 1000 μm, lay a piece of graphene paper with a through-hole array obtained in step 1 on the TA15 titanium alloy powder layer, and continue to overlap and lay the titanium powder layer and the graphene paper with a through-hole array obtained in step 1, with each group of laying being a layer, and laying a total of 20 layers to obtain a layered blank for powder metallurgy;

[0068] Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2, with the vacuum degree of vacuum hot pressing not higher than 10 -2 Pa, sintering temperature of 1300 ° C, pressure of 50 MPa, and holding time of 1 h to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure and a thickness of 14 mm.

[0069] The thermal conductivity and graphene content of the layered titanium-based composite materials prepared in Examples 1 to 6 were respectively tested, and the results are shown in Table 1.

[0070] Table 1

[0071]

[0072] From the comparison of the data in Table 1, it can be seen that the present invention achieves a significant improvement in thermal conductivity at a lower graphene content, breaking through the thermal conductivity bottleneck of titanium-based composite materials.

[0073] The room temperature tensile plasticity of pure titanium material, layered titanium-based composite materials prepared in Example 1 and Example 2 was tested respectively. The results are as follows: Figure 4 As shown in the figure, the titanium-based composite material prepared with 20 μm thick graphene paper still maintains a tensile plasticity of nearly 5% at room temperature, showing good comprehensive performance.

[0074] The method for preparing a layered titanium-based composite material provided by this invention offers high flexibility and designability, enabling precise control of the thickness of the graphene paper, the thickness of the titanium powder layer, and the number of overlapping layers, based on the actual mechanical performance requirements of the product. This method not only optimizes the material's overall performance but also significantly expands its application areas.

Claims

1. A method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure, characterized in that: Here are the steps: Step 1: forming a through-hole array on the graphene paper by laser marking; Step 2: Laying titanium powder layers and the graphene paper with through-hole arrays obtained in step 1 in an overlapping manner in a mold, with each layer being a layer, and laying 20 to 30 layers in total to obtain a layered blank for powder metallurgy; Step 3: vacuum hot pressing and sintering the layered blank obtained in step 2 to obtain a high thermal conductivity layered titanium-based composite material with a continuous graphene structure.

2. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 1, characterized in that: Step 1: The through-hole array is an array of multiple through-hole structures arranged at a fixed interval. The diameter of the through-hole is 25-250 μm, and the distance between two adjacent through-holes is 0.25-1 mm.

3. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 1 or 2, characterized in that: The thickness of the graphene paper in step 1 is 10-100 μm.

4. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 3, characterized in that: The power of the laser marking in step 1 is 10-100W, the scanning speed is 30-500mm / s, and the scanning number is 1-3 times.

5. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 4, characterized in that: The thickness of the titanium powder layer in step 2 is 200-1000 μm.

6. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 5, characterized in that: In step 2, the titanium powder layer is made of pure titanium powder or titanium alloy powder; the particle size of the pure titanium powder or titanium alloy powder is 15-53 μm.

7. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 6, characterized in that: The titanium alloy powder is TC4 titanium alloy powder, TA15 titanium alloy powder or Ti60 titanium alloy powder.

8. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 7, characterized in that: The vacuum degree of the vacuum hot pressing sintering in step 3 is not higher than 10 -2 Pa, sintering temperature is 900~1300℃, pressure is 50MPa, and holding time is 1h.

9. The method for preparing a high thermal conductivity layered titanium-based composite material having a continuous graphene structure according to claim 8, characterized in that: The thickness of the layered titanium-based composite material obtained in step 3 is 2 to 50 mm.

10. A high thermal conductivity layered titanium-based composite material having a continuous graphene structure prepared by the preparation method according to any one of claims 1 to 9, characterized in that: The content of the graphene is 0.5-10 wt.%.

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