A method for in-situ deposition of three-dimensional network graphene reinforced titanium alloy composite

Abstract

The present application relates to the field of graphene reinforced titanium alloy composite material, in particular to a preparation method of in-situ deposition three-dimensional network graphene reinforced titanium alloy composite material, which comprises the following steps: firstly, three-dimensional network graphene is in-situ deposited on the surface of porous titanium through chemical vapor deposition process; then, titanium alloy melt is filled into the porous preform by using high vacuum melt infiltration process, after a period of heat preservation treatment, finally, three-dimensional network graphene reinforced titanium alloy composite material is obtained by quenching. The three-dimensional network graphene reinforced titanium alloy composite material prepared by the present application has good interface combination and dense structure, by introducing graphene in the composite material, not only the load transmission effect is achieved, but also the part of TiC particles formed at the interface can make the crack deflect and hinder the crack propagation.

Description

Technical Field

[0001] This invention relates to the field of graphene-reinforced titanium alloy composites, specifically a method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composites. Background Technology

[0002] Titanium and titanium alloys are widely used in aerospace, automotive equipment, and biomedicine due to their excellent mechanical properties, including high strength, high toughness, and high impact resistance. However, with the continuous advancement of science and technology, higher requirements are being placed on the performance of raw materials for key components. Single titanium and titanium alloy materials can no longer meet the needs of practical applications. To further improve the performance of titanium alloys, titanium alloy composites have attracted widespread attention and research. Graphene, a two-dimensional material with ultra-high strength, high specific surface area, and excellent flexibility, can theoretically meet the requirements of interfacial strengthening, effective load transfer, and multivariate strain coordination in composite materials. Therefore, two-dimensional flexible graphene is an ideal reinforcing phase for titanium alloy composites.

[0003] In recent years, scholars from various countries have conducted extensive research on graphene-reinforced titanium alloy composites, preparing a series of graphene-reinforced titanium alloy composites with different compositions. Common systems include graphene-reinforced pure titanium composites and graphene-reinforced TC4 composites. However, the preparation methods for these graphene-reinforced titanium alloy composites are all traditional powder metallurgy methods, which involve sequentially mixing graphene sheets and titanium alloy powders and then sintering them. Due to the large specific surface area and strong interlayer van der Waals forces of graphene, agglomeration easily occurs during the powder mixing process, resulting in uneven dispersion of graphene in the matrix and limiting the material's performance to some extent. Therefore, although the strength of the composite material is improved, its plasticity and toughness are significantly reduced, greatly limiting its practical applications. Therefore, the ability to prepare graphene-reinforced titanium alloy composites with uniform graphene distribution has significant technical and application value. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, which is prepared by chemical vapor deposition and high-vacuum melt infiltration process.

[0005] The technical solution described in this invention is as follows: A method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, wherein the composite material is prepared by chemical vapor deposition combined with high vacuum melt infiltration process.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: Step (1) Select porous titanium as the substrate, place it in a quartz tube, and place it together in a horizontal tube furnace. Perform chemical vapor deposition in an atmosphere of methane, hydrogen and argon to form a three-dimensional network graphene on the sample surface. Step (2) Select Ti as the component 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The alloy is used as a melt material for high vacuum melt infiltration, and alloy ingots are prepared by vacuum arc melting. Step (3) Using a high-vacuum melt infiltration process, the alloy melt of the infiltrated material is filled into the gaps of the porous preform. After holding at a temperature for 3 to 10 minutes, it is rapidly quenched and cooled to obtain a three-dimensional network graphene-reinforced titanium alloy composite material.

[0007] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, in step (1), the method for characterizing graphene is: analyzing the graphene on the porous titanium surface by Raman spectroscopy.

[0008] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, in step (1), the porous titanium has a pore size of 100~150 μm, a porosity of 30~70%, a diameter of Φ5~20 mm, and a thickness of 2~5 mm.

[0009] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, in step (1), the porous titanium is ultrasonically cleaned in acetone and ethanol for 40 min in sequence before chemical vapor deposition, and then dried in an oven at 80 ℃ for 1 h.

[0010] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, the chemical vapor deposition method involves heating the substrate to 1040 °C in an atmosphere of hydrogen with a volume flow rate of 100-200 sccm and argon with a volume flow rate of 500 sccm, annealing for 5 min, and then introducing methane with a volume flow rate of 5 sccm to initiate graphene growth for 10 min under normal pressure.

[0011] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, after the matrix has undergone chemical vapor deposition, the sample is rapidly cooled to room temperature at a cooling rate of 100 °C / min in a protective atmosphere of argon and hydrogen.

[0012] Furthermore, the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material uses high-purity Ti, Zr, Ni, Cu, and Be metals with a purity >99.8%, and prepares a specific composition Ti by arc melting in a high-purity argon atmosphere containing Ti. 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 Alloy ingots undergo at least four repeated melting processes to ensure chemical homogeneity.

[0013] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, step (3) specifically involves: using a stacking method, stacking the deposited porous titanium samples and then compacting them to form a preform. Ti 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The alloy ingot and preform are placed in a stainless steel tube and preheated to a temperature above the alloy liquidus line under high vacuum. Then, the alloy melt is filled into the porous preform by pressure infiltration.

[0014] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, a compressed sample is cut from the three-dimensional network graphene-reinforced titanium alloy composite material obtained in step (3). The diameter of the compressed sample is Φ5 mm and the height is 10 mm. Before the experiment, the base surface of the sample is carefully polished to make it parallel to each other and perpendicular to the side surface. -4 The specimen was uniformly compressed at a strain rate of / s until it fractured. After fracture, samples were taken to observe the microstructure of the deformation. The interface was well bonded, the structure was dense, and there were no obvious internal defects.

[0015] Furthermore, in the above-mentioned method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, the compressive yield strength of the compressed sample is 1225 ± 20 MPa, the compressive strength is 1506 ± 20 MPa, and the compressive plasticity is 6.75 ± 0.2%.

[0016] The advantages and beneficial effects of this invention are: (1) The three-dimensional network graphene-reinforced titanium alloy composite material described in this invention uses porous titanium as the matrix. First, three-dimensional network graphene is deposited in situ on the surface of porous titanium by chemical vapor deposition. Then, the alloy melt is filled into the porous titanium preform using a high-vacuum melt infiltration process, successfully preparing the three-dimensional network graphene-reinforced titanium alloy composite material. The process is simple, economical, and effective, and is expected to achieve industrial production. The high-vacuum melt infiltration process can reduce defects such as pores caused by traditional powder metallurgy processes. The prepared composite material has good interfacial bonding, dense structure, and no obvious internal defects.

[0017] (2) This invention utilizes chemical vapor deposition (CVD) to prepare uniformly distributed three-dimensional network graphene in situ on the surface of porous titanium, alleviating the problem of graphene agglomeration in traditional powder metallurgy processes. This method is novel in process, innovative in structure, and low in cost, and has broad application prospects for developing novel three-dimensional network graphene-reinforced titanium alloy composite materials.

[0018] (3) The three-dimensional network graphene-reinforced titanium alloy composite material described in this invention exhibits excellent compressive mechanical properties. Through chemical vapor deposition, uniformly distributed three-dimensional network graphene is deposited in situ within the composite material. High-vacuum melt infiltration technology ensures good interfacial bonding, a dense structure, and the absence of significant internal defects. This significantly improves the compressive yield strength, compressive strength, and compressive plasticity of the composite material. It alleviates the problem of graphene agglomeration in traditional powder metallurgy processes and has broad application prospects for developing novel three-dimensional network graphene-reinforced titanium alloy composite materials. Attached Figure Description

[0019] Figure 1 The microstructure, X-ray diffraction pattern, and Raman spectrum of porous titanium after chemical vapor deposition in Example 1 are shown. Figure 2 The initial microstructure and X-ray diffraction pattern of the porous titanium in Comparative Example 1; Figure 3 The as-cast microstructure and X-ray diffraction pattern of the composite material in Example 1; Figure 4 The as-cast microstructure and X-ray diffraction pattern of the composite material in Comparative Example 1; Figure 5 The compression engineering stress-strain curves of the two composite materials in Example 1 and Comparative Example 1 are shown. Figure 6 The image shows the scanning electron microscope (SEM) morphology of the composite material after compression failure in Example 1. Detailed Implementation

[0020] In the specific implementation process, the preparation method of three-dimensional network graphene reinforced titanium alloy composite material is as follows: Porous pure titanium with a pore size of 100~150 μm was selected as the matrix structure. Three-dimensional network graphene was deposited in situ on the surface of porous titanium using chemical vapor deposition in an atmosphere of methane, hydrogen and argon. The uniform distribution of graphene was achieved by controlling the process parameters. The graphene on the surface of porous titanium was analyzed by Raman spectroscopy.

[0021] The alloy composition used in high vacuum melt infiltration is Ti. 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The raw materials are high-purity Ti, Zr, Ni, Cu, and Be metals with a purity >99.8%. Alloy ingots are prepared by arc melting in a high-purity argon atmosphere (volume purity 99.999%, 0.01~0.1 MPa). The alloy ingots are repeatedly melted at least four times to ensure the uniformity of the components.

[0022] A preform was fabricated by stacking deposited porous titanium samples using a layering method and then compacting them tightly. Ti 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 Alloy ingots and preforms were placed in stainless steel tubes and preheated to a temperature above the alloy liquidus line under high vacuum. Then, the alloy melt was pressure-infiltrated into the porous preform, held at this temperature for a certain time, and then rapidly quenched and cooled in supersaturated brine to prepare a three-dimensional network graphene-reinforced titanium alloy composite material. Compressed samples with a diameter of Φ5 mm and a height of 10 mm were cut from the composite material, and their microstructure was characterized.

[0023] Microstructural analysis revealed that three-dimensional network graphene was deposited in situ on the porous titanium surface via chemical vapor deposition, and the graphene exhibited low structural defects. Mechanical testing showed that the introduction of graphene into the composite material improved its compressive yield strength, compressive strength, and compressive plasticity.

[0024] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings and examples. Example 1

[0025] Porous titanium with a pore size of 150 μm, a porosity of 30%, a diameter of Φ10 mm, and a thickness of 3 mm was selected as the substrate. The porous titanium was ultrasonically cleaned in acetone and ethanol for 40 min, and then dried in an oven at 80 ℃ for 1 h. The treated porous titanium was placed in a quartz tube and then placed in a horizontal tube furnace, heated to 1040 ℃ under a hydrogen atmosphere with a volumetric flow rate of 200 sccm and an argon atmosphere with a volumetric flow rate of 500 sccm. After annealing for 5 min, CH4 with a volumetric flow rate of 5 sccm was introduced to initiate graphene growth at atmospheric pressure for 10 min. After growth, the sample was rapidly cooled to room temperature at a cooling rate of 100 ℃ / min under a hydrogen and argon protective atmosphere, forming a three-dimensional network of graphene on the porous titanium surface.

[0026] Selected component is Ti 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The alloy is used as the melt material for high-vacuum melt infiltration. The raw materials are high-purity Ti, Zr, Ni, Cu, and Be metals with a purity >99.8%. The raw materials are arranged in order of decreasing melting point from top to bottom, and the furnace pressure is reduced to 3.5 × 10⁻⁶ using mechanical and molecular pumps. -3 The pressure was increased to approximately 0.05 MPa by introducing high-purity argon gas. Under argon protection, alloy ingots were prepared by arc melting. The ingots were repeatedly melted four times to ensure the homogeneity of the components. Using a stacking method, deposited porous titanium samples were stacked and then tightly compacted to form a preform. Ti... 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 Alloy ingots and preforms are placed in stainless steel tubes and preheated to a temperature above the alloy liquidus line under high vacuum. Then, the alloy melt is filled into the porous preform by pressure infiltration, held at that temperature for 5 minutes, and then rapidly quenched and cooled in supersaturated brine to prepare a three-dimensional network graphene-reinforced titanium alloy composite material.

[0027] A compressed sample with a diameter of Φ5 mm and a height of 10 mm was cut from the composite material using wire electrical discharge machining and a high-speed saw. The compressed sample was then ground and polished with sandpaper and polishing liquid to facilitate accurate characterization of the material's microstructure.

[0028] Microstructure characterization of porous titanium after chemical vapor deposition. Figure 1The microstructure of the porous titanium surface appears as if coated with a thin film, indicating that chemical vapor deposition (CVD) is effective under these parameters. X-ray diffraction analysis revealed that it consists of two phases: α-Ti and TiC. Raman spectroscopy confirmed the formation of high-quality graphene on the porous titanium surface. After high-vacuum melt infiltration, the microstructure and X-ray diffraction analysis of the composite material were performed. Figure 3 The microstructure shows that the melt uniformly penetrates the pores of the porous titanium, with no pores or other defects at the interface, indicating good infiltration. X-ray diffraction analysis shows that the crystallization peaks of α-Ti and β-Ti in the composite material are superimposed on the diffuse scattering peaks of the amorphous phase, and some TiC crystallization peaks are also present.

[0029] Comparative Example 1 Porous titanium with a pore size of 150 μm, a porosity of 30%, a diameter of Φ10 mm, and a thickness of 3 mm was selected as the matrix. The porous titanium was ultrasonically cleaned in acetone and ethanol for 40 min each, and then dried in an oven at 80 ℃ for 1 h.

[0030] Selected component is Ti 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The alloy was used as the melt material for high-vacuum melt infiltration. The raw materials were high-purity Ti, Zr, Ni, Cu, and Be metals with a purity >99.8%. The raw materials were arranged in order of decreasing melting point from top to bottom, and the furnace pressure was reduced to 3.5 × 10⁻⁶ using mechanical and molecular pumps. -3 The pressure was increased to approximately 0.05 MPa by introducing high-purity argon gas. Under argon protection, alloy ingots were prepared by arc melting. The ingots were repeatedly melted four times to ensure the homogeneity of the components. Using a stacking method, porous titanium samples were stacked and then tightly compacted to form a preform. Ti... 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 Alloy ingots and preforms are placed in stainless steel tubes and preheated to a temperature above the alloy liquidus line under high vacuum. Then, the alloy melt is filled into the gaps of the porous preform by pressure infiltration, held at that temperature for 5 minutes, and then rapidly quenched and cooled in supersaturated brine to prepare a three-dimensional network graphene-reinforced titanium alloy composite material.

[0031] A compressed sample with a diameter of Φ5 mm and a height of 10 mm was cut from the composite material using wire electrical discharge machining and a high-speed saw. The compressed sample was then ground and polished with sandpaper and polishing liquid to facilitate accurate characterization of the material's microstructure.

[0032] Microstructure characterization and X-ray diffraction analysis of porous titanium were performed. Figure 2 It can be seen that it is composed of the α-Ti phase. After high-vacuum melt infiltration, the microstructure and X-ray diffraction analysis of the composite material were performed. Figure 4 The microstructure shows that the melt uniformly penetrates the pores of the porous titanium, with no pores or other defects at the interface, indicating good infiltration. X-ray diffraction analysis shows that the crystalline peaks of α-Ti and β-Ti in the composite material are superimposed on the diffuse scattering peaks of the amorphous phase.

[0033] Figure 5 The compressive stress-strain curves of the composite materials of Example 1 and Comparative Example 1 are shown. It can be seen that the yield strength of Comparative Example 1 is 1028 ± 15 MPa, the compressive strength is 1252 ± 18 MPa, and the compressive plasticity is 6.08 ± 0.1%. The composite material in Example 1 has a higher yield strength of 1225 ± 20 MPa, a compressive strength of 1506 ± 20 MPa, and a compressive plasticity of 6.75 ± 0.2%. Compared with the composite material in Comparative Example 1, the three-dimensional network graphene has a good reinforcing effect.

[0034] Figure 6 The image shows the scanning electron microscope (SEM) morphology of the composite material from Example 1 after compression failure, revealing dimples and deflection effects on the fracture surface. Since cracks always propagate along the path of least energy consumption, they tend to pin, bifurcate, or bypass the hard reinforcing phase. Combined with energy dispersive spectroscopy (EDS) analysis, it was found that TiC blocked the crack propagation process, causing crack deflection. Furthermore, the EDS analysis revealed fragmented graphene on the fracture surface, indicating that graphene not only transfers the load during compression but also bears a portion of it. The pull-out effect of graphene and the crack propagation-impeding effect of TiC consume the energy required for crack formation and propagation, resulting in a significant increase in strength.

[0035] The results of the embodiments show that the present invention prepares in-situ deposited three-dimensional network graphene-reinforced titanium alloy composites through chemical vapor deposition and high-vacuum melt infiltration processes. The three-dimensional network graphene-reinforced titanium alloy composites prepared by the present invention exhibit good interfacial bonding and a dense structure. By introducing graphene into the composite material, it not only transfers the load but also, through the formation of some TiC particles at the interface, deflects cracks, thereby hindering crack propagation. The compressive yield strength of the composite material increases from 1028 ± 15 MPa to 1225 ± 20 MPa, the compressive strength increases from 1252 ± 18 MPa to 1506 ± 20 MPa, and the compressive plasticity increases from 6.08 ± 0.1% to 6.75 ± 0.2%. This invention has significant value for the preparation of novel three-dimensional network graphene-reinforced titanium alloy composites and the practical application of lightweight, high-strength materials.

Claims

1. A method for preparing an in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material, characterized in that, The composite material was prepared using chemical vapor deposition and high-vacuum melt infiltration processes, and the specific steps are as follows: Step (1) Select porous titanium as the substrate and place it in a quartz tube. Place it together in a horizontal tube furnace and perform chemical vapor deposition in an atmosphere of methane, hydrogen and argon to form a three-dimensional network graphene on the sample surface. Step (2) Select Ti as the component 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The alloy is used as a melt material for high vacuum melt infiltration, and alloy ingots are prepared by vacuum arc melting. Step (3) Using a high-vacuum melt infiltration process, the alloy melt of the infiltrated material is filled into the gaps of the porous preform. After holding at a temperature for 3 to 10 minutes, it is rapidly quenched and cooled to obtain a three-dimensional network graphene-reinforced titanium alloy composite material.

2. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, In step (1), the graphene on the porous titanium surface is analyzed by Raman spectroscopy.

3. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, The porous titanium has a pore size of 100~150 μm, a porosity of 30~70%, a thickness of 2~5 μm, and a diameter of Φ5~20 mm.

4. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, Before chemical vapor deposition, porous titanium was ultrasonically cleaned in acetone and ethanol for 40 min in sequence, and then dried in an 80 ℃ drying oven for 1 h.

5. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, The chemical vapor deposition method involves heating the substrate to 1040 °C in an atmosphere of hydrogen with a volumetric flow rate of 100-200 sccm and argon with a volumetric flow rate of 500 sccm, annealing for 5 min, and then introducing methane with a volumetric flow rate of 5 sccm to initiate graphene growth for 5 min at atmospheric pressure.

6. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 5, characterized in that, After chemical vapor deposition, the sample was rapidly cooled to room temperature at a cooling rate of 100 °C / min in a protective atmosphere of argon and hydrogen.

7. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, Ti with a specific composition was prepared by arc melting using high-purity Ti, Zr, Ni, Cu, and Be metals with a purity >99.8% in a high-purity argon atmosphere containing Ti. 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 Alloy ingots, which have undergone at least four repeated melting processes to ensure chemical homogeneity.

8. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, Step (3) involves the following specific process: using a stacking method, deposited porous titanium samples are stacked and then compacted to form a preform, and Ti is then placed on top of the preform. 32.8 Zr 30.2 Ni 5.3 Cu9Be 22.7 The alloy ingot and preform are placed in a stainless steel tube and preheated to a temperature above the alloy liquidus line under high vacuum. Then, the alloy melt is filled into the porous preform by pressure infiltration.

9. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 1, characterized in that, A compression sample was cut from the three-dimensional network graphene-reinforced titanium alloy composite material obtained in step (3). The diameter of the compression sample was Φ5 mm and the height was 10 mm. Before the experiment, the base surface of the sample was carefully polished to make it parallel to each other and perpendicular to the side surface. -4 The specimen was uniformly compressed at a strain rate of / s until it fractured. After fracture, samples were taken to observe the microstructure of the deformation. The interface was well bonded, the structure was dense, and there were no obvious internal defects.

10. The method for preparing in-situ deposited three-dimensional network graphene-reinforced titanium alloy composite material according to claim 9, characterized in that, The compressive yield strength of the compressed sample was 1225 ± 20 MPa, the compressive strength was 1506 ± 20 MPa, and the compressive plasticity was 6.75 ± 0.2%.

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