A graphene oxide-reinforced titanium matrix composite based on selective laser melting forming and a preparation method thereof

Abstract

The present invention discloses a preparation method of a graphene oxide reinforced titanium matrix composite based on selective laser melting forming. In the present invention, CTAB is used to perform surface functionalization treatment on the surface of TC4, and a technology combining "ultrasonic dispersion + electrostatic adsorption self-assembly" is adopted for powder mixing. Subsequently, a selective laser melting technology is used to form the GO / TC4 composite material, which not only ensures the fluidity of the composite powder, but also ensures the original structure of GO in the formed GO / TC4 composite material, and is uniformly distributed in the matrix and forms an interface bond with moderate strength with the matrix.

Description

Technical Field

[0001] The present invention relates to a titanium matrix composite reinforced by two-dimensional nanomaterial graphene oxide, belonging to the technical field of additive manufacturing. Background Art

[0002] Titanium alloys have the characteristics of low density, high specific strength, good corrosion resistance, etc., and can effectively improve the thrust-to-weight ratio of engines and reduce energy consumption. They are widely used in aircraft structural components such as fuselages and landing gears, and aero-engine components such as fan blades, compressor blades, and casings. With the rapid development of modern science and technology and the national defense industry, higher requirements are put forward for the service performance of titanium alloys. Defects such as low elastic modulus and poor wear resistance limit their popularization and application, making the development of titanium alloys face a new round of challenges.

[0003] Titanium matrix composites can endow the matrix material with properties that single raw materials do not have by introducing reinforcing phase materials (ceramic particles, fibers such as carbides, oxides, nitrides, etc.), that is, they can significantly improve the wear resistance and high-temperature resistance of titanium alloys while obtaining higher strength and elastic modulus. It is one of the main future research directions of aerospace materials. At present, graphene has attracted wide attention as a metal matrix reinforcing phase due to its unique single-atom layer structure, which endows graphene with excellent mechanical properties (fracture strength up to 130 GPa, Young's modulus about 1100 GPa), thermal conductivity (thermal conductivity about 5000 W / m·K), and electrical conductivity (electron mobility reaches 200000 cm 2 / V·s), and has a large specific surface area of about 2630 m 2 g -1 .

[0004] Among them, graphene oxide (GO), as a functionalized graphene derivative, not only has the inherent properties of graphene, but also has the characteristics of high Young's modulus, excellent thermal conductivity and fracture resistance. In addition, due to the large number of hydroxyl, carboxyl and epoxy groups on the edges and surfaces of graphene oxide, these oxygen-containing functional groups are beneficial to the effective dispersion of GO in aqueous and organic solutions, thus largely alleviating the problem of easy aggregation of two-dimensional nanomaterials. Therefore, using GO as the reinforcing phase of titanium matrix composites to make up for the defects of low elastic modulus, poor wear resistance and poor thermal conductivity of the TC4 matrix has broad prospects for promoting the application of titanium matrix composites in key equipment.

[0005] Selective Laser Melting (SLM) technology is one of the most widely used metal additive manufacturing technologies at present. Using laser as the energy source, near-net shaping of complex metal components can be achieved through this layer-by-layer powder spreading - selective melting - solidification stacking method. It has characteristics such as a large temperature gradient and a fast cooling rate, making the microstructure of the material significantly different from the equilibrium state. For example, fine grains, increased solid solubility, and the appearance of new metastable phases have great potential in the field of preparing high-performance titanium matrix composites, and are mainly used in the preparation of precision components such as aerospace and automotive molds. Compared with traditional preparation processes, the specimens prepared by SLM show obvious advantages in terms of mechanical properties and microtopography.

[0006] However, at present, titanium matrix composites and their preparation methods still have the following defects:

[0007] (1) At present, the reinforcing phases of titanium matrix composites are mainly ceramic particles and fibers, and the added content is relatively high and the density is relatively large. Under this premise, although ceramic particle- and fiber-reinforced titanium matrix composites can improve the material properties to a certain extent, they weaken the excellent high specific strength of the titanium alloy matrix to a certain extent.

[0008] (2) At present, titanium matrix composites are mainly prepared by powder metallurgy and casting methods, but the composites prepared by these two methods have coarse grains and uneven microstructures, thus affecting the mechanical properties of the formed parts. Summary of the Invention

[0009] In view of the above technical deficiencies and other problems, the present invention proposes a selective laser melting technology to form a graphene oxide-reinforced titanium matrix composite with excellent mechanical properties and wear resistance and its preparation method. Using graphene oxide (GO) and TC4 powder as the original powders, this composite material is prepared by selective laser melting technology to develop a two-dimensional nano-reinforced composite material with excellent mechanical properties, good wear and corrosion resistance, and high temperature resistance.

[0010] The technical solution to achieve the object of the present invention is: A graphene oxide-reinforced titanium matrix composite based on selective laser melting forming and its preparation method, including:

[0011] (1) Add TC4 powder to cetyltrimethylammonium bromide (CTAB) solution, ultrasonic and mechanically stir for a period of time, and add an appropriate amount of absolute ethanol to the centrifuged suspension;

[0012] (2) Drop the solution obtained in step (1) into the graphene oxide (GO) nanosheet dispersion, ultrasonic for a period of time, and let it stand until the supernatant is completely transparent;

[0013] (3) Vacuum-dry the solution containing the composite powder in step (2) until the ethanol completely volatilizes, and grind the obtained composite powder.

[0014] (4) Use the composite powder obtained in step (3) to prepare a graphene oxide-reinforced titanium matrix composite by selective laser melting forming.

[0015] Preferably, in step (1), to ensure the powder fluidity, the TC4 is spherical powder with a particle size of ~15 - 53 μm.

[0016] Preferably, in step (1), ultrasonically and mechanically stir for 30 min; the TC4 powder is vacuum-dried, with a drying time of 12 h and a temperature of 80 °C.

[0017] Preferably, the mass ratio of TC4 to cetyltrimethylammonium bromide is 1000:1.

[0018] Preferably, in step (2), the particle size of the graphene oxide nanosheets is 0.55 - 1.2 nm and the purity is 99.9%.

[0019] Preferably, the mass ratio of graphene oxide to TC4 is 5 - 20:1000, preferably 5 - 10:1000.

[0020] Preferably, in step (2), ultrasonically stir for 2 h and let stand for 24 h until the supernatant is completely transparent.

[0021] Preferably, in step (3), the vacuum-drying temperature is 80 °C.

[0022] Preferably, in step (4), the process parameters of selective laser melting forming are: laser power 100 W, scanning speed 500 mm / s, scanning spacing 70 μm, and layer thickness 25 μm.

[0023] Compared with the prior art, the advantages of the present invention are as follows: The present invention uses a technology combining "ultrasonic dispersion + electrostatic adsorption self-assembly" for powder mixing, and then selects laser melting technology to form GO / TC4 composites. Compared with the TC4 samples without graphene addition, the hardness and elastic modulus of the 0.5wt.% GO / TC4 composites are increased by ~5.4% and ~10.4% respectively, and the anti-wear performance is increased by ~33.8%. The main reasons for the performance improvement: Generally, metal powders suitable for forming by selective laser melting technology must have good powder fluidity (sphericity). Compared with the existing ball milling powder mixing, the method of electrostatic adsorption self-assembly for mixing powders can not only ensure the sphericity of TC4 powders, but also perfectly retain the two-dimensional characteristics of the reinforcing phase. During the powder mixing process, the reinforcing phase will not have large losses, enabling the two-dimensional nano-reinforcing phase to be uniformly dispersed in the TC4 matrix, which is a prerequisite for the formed composites to have excellent performance. However, when the GO content increases, local agglomeration will occur, so the density, elastic modulus, and wear resistance of the composites first increase and then decrease with the increase of the GO content. Description of the Drawings

[0024] Figure 1 It is a schematic diagram of the mixing and forming process of GO and TC4 powders of the present invention.

[0025] Figure 2 It is the SEM diagram of the composite powders obtained in Examples 2-5 of the present invention, where (a) 0.5wt.% GO / TC4 composite; (b) 1wt.% GO / TC4 composite; (c) 1.5wt.% GO / TC4 composite; (d) 2wt.% GO / TC4 composite.

[0026] Figure 3 It is the SEM diagram of the composites obtained in Examples 1-5 of the present invention, where (a) pure TC4 sample; (b) 0.5wt.% GO / TC4 composite; (c) 1wt.% GO / TC4 composite; (d) 1.5wt.% GO / TC4 composite; (e) 2.0wt.% GO / TC4 composite.

[0027] Figure 4 It is the OM diagram of the composites obtained in Examples 1-5 of the present invention or the SEM diagram of the remelting zone, where (a) OM diagram of the microstructure of 0.5wt.% GO / TC4 composite; (b) OM diagram of the microstructure of 1wt.% GO / TC4 composite; (c) SEM diagram of the remelting zone of 0.5wt.% GO / TC4 composite; (d) SEM diagram of the remelting zone of 1wt.% GO / TC4 composite; (e) SEM diagram of the molten pool zone of 0.5wt.% GO / TC4 composite; (f) SEM diagram of the molten pool zone of 1wt.% GO / TC4 composite.

[0028] Figure 5 Typical instrumented micro-indentation pressure-displacement curves of GO / TC4 composites with different contents in Examples 1-5.

[0029] Figure 6 Friction property diagrams of GO / TC4 composites with different contents in Examples 1-5, where (a) is the friction coefficient curve diagram; (b) is the wear rate diagram. Detailed implementation manners

[0030] To better understand the technical content of the present invention, specific embodiments are given below in conjunction with the accompanying drawings for illustration.

[0031] In the present invention, various aspects of the present invention are described with reference to the accompanying drawings, in which many illustrative embodiments are shown. The embodiments of the present invention are not necessarily intended to cover all aspects of the present invention. It should be understood that the various concepts and embodiments introduced above, as well as those described in more detail below, can be implemented in any of a number of ways, because the concepts and embodiments disclosed in the present invention are not limited to any implementation manner. Additionally, some aspects disclosed in the present invention can be used alone, or in any suitable combination with any other aspects disclosed in the present invention.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs; the term "and / or" as used herein includes any and all combinations of one or more of the related listed items.

[0033] For those conditions not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments whose manufacturers are not specified, they are all conventional products that can be obtained through commercial purchase.

[0034] As used herein, the term "about" is used to provide flexibility and imprecision associated with a given term, measurement, or value. Those skilled in the art can easily determine the degree of flexibility of a specific variable.

[0035] As used herein, the term "at least one of..." is intended to be synonymous with "one or more of...". For example, "at least one of A, B, and C" clearly includes only A, only B, only C, and their respective combinations.

[0036] Concentrations, amounts, and other numerical data may be presented herein in a range format. It should be understood that such range formats are used merely for convenience and brevity and should be interpreted flexibly as including not only the values explicitly recited as the limits of the range but also all individual values or sub-ranges subsumed within the stated range as if each value and sub-range were explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted as including not only the explicitly recited limits of 1 to about 4.5 but also the individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges that recite only one numerical value, such as "less than about 4.5", which should be interpreted as including all of the above values and ranges. In addition, this interpretation should apply regardless of the breadth of the range or feature being described.

[0037] In this invention, CTAB is used to perform surface functionalization on the surface of TC4 and is combined with negatively charged GO mixed powder. Generally, metal powders suitable for forming by selective laser melting technology must have good powder fluidity (sphericity). Compared with the existing ball milling mixed powder, the method of electrostatic adsorption self-assembly for mixing powders can not only ensure the sphericity of TC4 powder but also perfectly retain the two-dimensional characteristics of the reinforcing phase, and there will be no significant loss of the reinforcing phase during the powder mixing process. Additionally, the prerequisite for obtaining a composite material with excellent performance is that the reinforcing phase is uniformly dispersed in the TC4 matrix, maintaining its original two-dimensional structural characteristics through powder mixing process and high-temperature forming process, etc., and the reinforcing phase GO should form an interfacial bond with moderate strength with the matrix phase TC4, which is beneficial for stress to be effectively transferred from the matrix phase to the reinforcing phase. For the above reasons, we selected the method of electrostatic adsorption self-assembly for powder mixing and the selective laser melting technology with a rapid melting and solidification process to prepare GO / TC4 composite materials, which not only ensured the fluidity of the composite powder but also ensured the original structure of GO in the formed GO / TC4 composite material, and was uniformly distributed in the matrix and formed an interfacial bond with moderate strength with the matrix.

[0038] Combined Figure 1 , the steps for preparing graphene oxide reinforced titanium matrix (TC4) composite materials in this invention are as follows:

[0039] This invention prepared GO / TC4 composite materials with five compositions (0 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%), and the specific contents can be seen in Table 1. The preparation process is as follows:

[0040] Table 1. Composition table of MXene / Cu composite material powder content

[0041]

[0042] (1) Preparation of graphene oxide nanosheet dispersion

[0043] a. Pour the weighed graphene oxide GO into a beaker with a volume of 1000 ml according to Table 1, and then add

[0044] absolute ethanol up to the 300 ml scale line of the beaker;

[0045] b. After the solution is prepared, cover the mouth of the cup with a plastic film and then carry out ultrasonic treatment. Ultrasonic for 24 h at 40 °C. After the ultrasonic dispersion is completed, the dispersion is ready for use.

[0046] (2) Functionalized TC4 powder

[0047] a. Vacuum dry the weighed 5 kg of TC4 metal powder. Set the time to 12 h and the temperature to 80 °C;

[0048] b. After drying is completed, divide the 5 kg of TC4 powder into five equal parts, each part being 1 kg;

[0049] c. Weigh four portions of 1 g of cetyltrimethylammonium bromide (CTAB), add 500 ml of absolute ethanol to each of them, and then

[0050] carry out magnetic stirring at 40 °C until completely dissolved and transparent;

[0051] d. According to Table 1, add the weighed TC4 powder to the CTAB solution while performing ultrasonic and mechanical stirring operations

[0052] for 30 min;

[0053] e. Pour the solution in d above into a centrifuge tube, and centrifuge at 4000 rpm / min in a centrifuge (LC-LX-L40B, Shanghai Lichen Bangxi Instrument Technology Co., Ltd.) for 30 min. After centrifugation, remove the supernatant, and collect the

[0054] suspension at the bottom of the centrifuge tube. Pour it into a beaker with a volume of 2000 ml, and add absolute ethanol up to the 700 ml scale line of the beaker; f. Dropwise add the solution in e to the GO dispersion, ultrasonic for 2 h, and let it stand for 24 h until the supernatant is completely transparent, indicating that

[0055] GO is completely electrostatically adsorbed on the TC4 matrix powder particles.

[0056] g. Put the solution containing the composite powder into a vacuum drying oven and vacuum dry it at 80 °C until all the ethanol has evaporated, and grind the powder for use.

[0057] (3) Composite material forming

[0058] The composite powder is subjected to selective laser melting forming, and 3D printing is carried out according to the following parameters: laser power 100W, scanning speed 500mm / s, scanning spacing 70μm, layer thickness 25μm to obtain a bulk graphene oxide-reinforced titanium matrix composite. The forming steps are as Figure 1 shown.

[0059] Example 1

[0060] Take 1 kg of TC4 powder as the original powder without adding graphene oxide nanosheets, and put the dried powder into a selective laser melting equipment for printing and forming. The printing parameters are set as follows: laser power 100W, scanning speed 500mm / s, scanning spacing 70μm, layer thickness 25μm.

[0061] Example 2

[0062] Take 1 kg of TC4 powder and graphene oxide nanosheets as the original powder, where the weight ratio of the oxygen graphene nanosheets is 0.5 wt.% (5 g). The graphene oxide nanosheets are ultrasonically dispersed at 40°C for 24 h to obtain a graphene oxide nanosheet dispersion. The cationic dispersant CTAB is magnetically stirred until the CTAB particles in the solution are completely dissolved. After adding TC4 powder to the CTAB solution, ultrasonic and mechanical stirring operations are carried out for 30 min, and then the supernatant is removed by centrifugation. Finally, the functionalized TC4 powder solution is dropped into the GO dispersion drop by drop, ultrasonically treated for 2 h, and then left standing for 24 h to enable sufficient electrostatic self-assembly. The composite powder is dried and ground to serve as the mixed powder required for printing. The dried powder is put into a selective laser melting equipment for printing and forming. The printing parameters are set as follows: laser power 100W, scanning speed 500mm / s, scanning spacing 70μm, layer thickness 25μm.

[0063] Example 3

[0064] Take 1 kg of TC4 powder and graphene oxide nanosheets as the original powder, where the weight ratio of the oxygen graphene nanosheets is 1 wt.% (10 g). The graphene oxide nanosheets are ultrasonically dispersed at 40°C for 24 h to obtain a graphene oxide nanosheet dispersion. The cationic dispersant CTAB is magnetically stirred until the CTAB particles in the solution are completely dissolved. After adding TC4 powder to the CTAB solution, ultrasonic and mechanical stirring operations are carried out for 30 min, and then the supernatant is removed by centrifugation. Finally, the functionalized TC4 powder solution is dropped into the GO dispersion drop by drop, ultrasonically treated for 2 h, and then left standing for 24 h to enable sufficient electrostatic self-assembly. The composite powder is dried and ground to serve as the required mixed powder for printing. The dried powder is put into a selective laser melting equipment for printing and forming. The printing parameters are set as follows: laser power 100W, scanning speed 500mm / s, scanning spacing 70μm, layer thickness 25μm.

[0065] Example 4

[0066] Take 1 kg of TC4 powder and graphene oxide nanosheets as the original powders, where the weight ratio of graphene oxide nanosheets is 1.5 wt.% (15 g). Ultrasonically disperse the graphene oxide nanosheets at 40 °C for 24 h to obtain a graphene oxide nanosheet dispersion. Magnetically stir the cationic dispersant CTAB until the CTAB particles in the solution are completely dissolved. After adding the TC4 powder to the CTAB solution, perform ultrasonic and mechanical stirring operations for 30 min, then centrifuge to remove the supernatant. Finally, dropwise add the functionalized TC4 powder solution into the GO dispersion, ultrasonically treat for 2 h, and then let it stand for 24 h to enable sufficient electrostatic self-assembly. Dry and grind the composite powder to obtain the mixed powder required for printing. Put the dried powder into a selective laser melting device for printing. The printing parameters are set as follows: laser power 100 W, scanning speed 500 mm / s, scanning spacing 70 μm, layer thickness 25 μm.

[0067] Example 5

[0068] Take 1 kg of TC4 powder and graphene oxide nanosheets as the original powders, where the weight ratio of graphene oxide nanosheets is 2 wt.% (20 g). Ultrasonically disperse the graphene oxide nanosheets at 40 °C for 24 h to obtain a graphene oxide nanosheet dispersion. Magnetically stir the cationic dispersant CTAB until the CTAB particles in the solution are completely dissolved. After adding the TC4 powder to the CTAB solution, perform ultrasonic and mechanical stirring operations for 30 min, then centrifuge to remove the supernatant. Finally, dropwise add the functionalized TC4 powder solution into the GO dispersion, ultrasonically treat for 2 h, and then let it stand for 24 h to enable sufficient electrostatic self-assembly. Dry and grind the composite powder to obtain the mixed powder required for printing. Put the dried powder into a selective laser melting device for printing. The printing parameters are set as follows: laser power 100 W, scanning speed 500 mm / s, scanning spacing 70 μm, layer thickness 25 μm.

[0069] Figure 2 In (a)-(d) are SEM images of the composite powders with different contents in Examples 2-5. From Figure 2 it can be seen that with the increase in the GO addition content, local agglomeration occurs. When the GO addition content is below 1 wt.%, the GO nanosheets tightly wrap around the outer surface of the TC4 powder particles, forming a strong interfacial bonding effect. However, when the GO addition content reaches above 1.5 wt.%, the GO nanosheets agglomerate severely, which is likely to lead to a decline in material properties. This shows that the ultrasonic dispersion technology can effectively disperse the agglomerated GO nanosheets, and the method of electrostatic adsorption self-assembly can make the GO nanosheets uniformly dispersed in the TC4 matrix powder, but the content of the added reinforcement cannot be too high.

[0070] Figure 3 They are SEM images of composites with different compositions formed by SLM in Examples 1-5. It can be seen that the cracks and pores in the materials increase with the increase of the GO content. When the content of the reinforcement GO is below 1 wt.%, no obvious defects appear in the microstructure diagram of the composite material. However, when the content of the reinforcement GO reaches more than 1.5 wt.%, obvious material defects occur because the graphene oxide nanosheets locally agglomerate, resulting in an increase in the porosity of the material structure.

[0071] Figure 4 In (a) and (b), they are OM images of the composites with two contents of 0.5 wt.% and 1 wt.% after corrosion. It can be seen from the figures that the metallography of the composite material is mainly composed of β phase and α' phase. From Figure 4 In (c), (d) and (e), (f), it can be seen that with the increase of the content of graphene oxide nanosheets, the grains of the composite material in the remelting zone and the microstructure of the molten pool are further refined, which plays a positive role in improving the performance of the material.

[0072] Table 2 lists the specific values of the relative density, Vickers hardness value and elastic modulus of the composite material samples with different GO contents. It can be seen from Table 2 that the relative density reaches the highest value of about 98.9% at the GO content of 0.5 wt.%. The microhardness of the samples increases with the increase of the GO content, and the highest HV 0.1 value is about 472.55, which is about 16.5% higher than that of the TC4 sample. From Figure 5 it can be seen that the elastic modulus of the material first increases and then decreases with the increase of the GO content, and reaches the highest value when the GO content is 0.5 wt.%, increasing by about 10.4%.

[0073] Table 2. Relative density, Vickers hardness value and indentation elastic modulus of composites with different GO contents

[0074]

[0075] Figure 6 In (a), it is the friction coefficient curve of the composite material samples with different GO contents. The curve is stable and the fluctuation is small. Experiments under a load of 5 N show that the friction coefficient of the material is the lowest when the GO content is 0.5 wt.%, about 0.35. From Figure 6 In (b), it can be seen that through experiments under a load of 5 N, it is found that the wear rate of the material is the lowest when the GO content is 0.5 wt.%, and the minimum wear rate is about 9.8×10 -5 mm 3 / Nm.

[0076] Therefore, the present invention uses the "technology combining ultrasonic dispersion and electrostatic adsorption self-assembly" to mix the composite material powder. By relying on the electrostatic adsorption self-assembly between the reinforcement and the matrix, the intrinsic characteristics (negatively charged functional groups) of the graphene oxide reinforcement are fully utilized. This method can perfectly retain the two-dimensional characteristics of the reinforcement phase, and there will be no significant loss of the reinforcement phase during the powder mixing process, improving the accuracy of theoretical analysis. After the powder mixing is completed, the composite material is prepared by selective laser melting technology, aiming to obtain a composite material with excellent mechanical properties and wear resistance.

Claims

1. A method for preparing a graphene oxide reinforced titanium-based composite material based on selective laser melting, characterized in that: The steps include: (1) Add TC4 powder to hexadecyltrimethylammonium bromide solution, ultrasonicate and mechanically stir for a period of time, and add an appropriate amount of anhydrous ethanol to the resulting suspension after centrifugation; (2) adding the solution obtained in step (1) dropwise into the graphene oxide nanosheet dispersion, ultrasonicating for a period of time, and standing until the supernatant becomes completely transparent; (3) vacuum drying the solution containing the composite powder in step (2) until the ethanol is completely volatilized, and grinding the obtained composite powder; (4) preparing a graphene oxide reinforced titanium-based composite material by selective laser melting of the composite powder obtained in step (3); Among them, the weight of graphene oxide nanosheets accounts for 0.5% of the total weight of TC4 and graphene oxide nanosheets.

2. The method according to claim 1, characterized in that In step (1), TC4 is a spherical powder with a particle size of 15-53 μm.

3. The method according to claim 1, characterized in that In step (1), ultrasonication and mechanical stirring are performed for 30 min; TC4 powder is vacuum dried for 12 h at a temperature of 80°C.

4. The method according to claim 1, characterized in that The mass ratio of TC4 to hexadecyltrimethylammonium bromide is 1000:

1.

5. The method according to claim 1, characterized in that In step (2), the particle size of the graphene oxide nanosheets is 0.55-1.2 nm and the purity is 99.9%.

6. The method according to claim 1, characterized in that In step (2), ultrasonication was performed for 2 h and the mixture was allowed to stand for 24 h until the supernatant was completely transparent.

7. The method according to claim 1, characterized in that In step (3), the vacuum drying temperature is 80°C.

8. The method according to claim 1, characterized in that In step (4), the process parameters of the selective laser melting forming are: laser power 100 W, scanning speed 500 mm / s, scanning spacing 70 µm, and layer thickness 25 µm.

9. A graphene oxide reinforced titanium-based composite material prepared by the method according to any one of claims 1 to 8.

Images