High-strength corrosion-resistant titanium alloy porous hydrophobic membrane

Abstract

The invention relates to the technical field of additive manufacturing, and provides a high-strength corrosion-resistant titanium alloy porous hydrophobic membrane which is obtained after powder is subjected to 3D printing, the powder comprises titanium alloy powder and titanium nitride powder, and the titanium alloy powder is composed of, by weight, 0.03%-0.1% of aluminum, 3.5%-7.8% of manganese, 3.6%-5.4% of cobalt, 0.02%-0.15% of silicon, 0.01%-0.08% of carbon, 0.002%-0.1% of oxygen, 0.012%-0.05% of nitrogen, 0.003%-0.115% of hydrogen and the balance titanium; the mass ratio of the titanium alloy powder to the titanium nitride powder is 100: (2.5-3.7). Through the technical scheme, the problem of poor tensile strength of the high-strength corrosion-resistant titanium alloy porous hydrophobic membrane in related technologies is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of additive manufacturing, and specifically, to a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane. Background Art

[0002] In the continuous development process of materials science, the research and development of high-performance materials has always been the core element for various industries to achieve technological breakthroughs and innovations. In recent years, with the increasingly stringent requirements for material properties in the industrial field, materials with multiple excellent characteristics have become a research hotspot, especially porous hydrophobic membranes. Porous hydrophobic membranes are commonly used in fields such as oil-water separation, seawater desalination, drug purification, oil purification, air purification, etc., among which high-strength and corrosion-resistant titanium alloy porous hydrophobic membranes have attracted much attention.

[0003] Superhydrophobic materials refer to materials with a water contact angle greater than 150° and a rolling angle less than 10° on the material surface, and can be applied in fields such as self-cleaning, anti-fogging, anti-icing, drag reduction, and oil-water separation. Superhydrophobic materials are usually constructed through two approaches. One is to modify low-surface-energy substances on the surface with micro-nano rough structures; the other is to construct micro-nano rough structures on the surface of substances with low surface energy.

[0004] There are many methods for preparing the superhydrophobic surface of superhydrophobic membrane materials, including etching, electrochemistry, chemical vapor deposition, template extrusion, electrospinning, chemical corrosion, phase separation, sol-gel, self-assembly, etc., but there are some defects in all of them. As a kind of rapid prototyping technology, 3D printing is a technology that constructs objects by layer-by-layer printing based on digital model files, using powdery metals or plastics and other bondable materials. This simple, fast, and environmentally friendly method for preparing ordered porous superhydrophobic membranes has good application value.

[0005] 3D printing technology, also known as additive manufacturing technology, can precisely control the stacking position and shape of materials, and achieve precise design and manufacturing of the pore structure of porous membranes. Using 3D printing technology to prepare high-strength and corrosion-resistant titanium alloy porous hydrophobic membranes can customize unique pore structures according to different application requirements, thereby optimizing the hydrophobic and mechanical properties of the membranes. In addition, 3D printing technology also has advantages such as short manufacturing cycle, high material utilization rate, and the ability to achieve personalized manufacturing, providing the possibility for large-scale production of high-performance corrosion-resistant titanium alloy porous hydrophobic membranes.

[0006] However, currently, the corrosion-resistant titanium alloy porous hydrophobic membranes prepared by 3D printing still need to improve in terms of tensile strength. To meet the growing demand for high-performance materials in various industries, it is of great practical significance to develop a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane prepared by 3D printing with significantly improved tensile strength. Summary of the Invention

[0007] The present invention provides a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane, which solves the problem of poor tensile strength of the high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane in the related art.

[0008] The technical solution of the present invention is as follows: The present invention provides a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane, which is obtained by 3D printing of powder. The powder includes titanium alloy powder and titanium nitride powder. The titanium alloy powder is composed of the following elements by weight percentage: aluminum 0.03% - 0.1%, manganese 3.5% - 7.8%, cobalt 3.6% - 5.4%, silicon 0.02% - 0.15%, carbon 0.01% - 0.08%, oxygen 0.002% - 0.1%, nitrogen 0.012% - 0.05%, hydrogen 0.003% - 0.115%, and the balance is titanium; The mass ratio of the titanium alloy powder to the titanium nitride powder is 100:2.5 - 3.7.

[0009] As a further technical solution, the mass ratio of manganese to cobalt is 1 - 1.5:1.

[0010] In the present invention, by adjusting the mass ratio of manganese to cobalt to 1 - 1.5:1, the tensile strength of the high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane is further improved.

[0011] As a further technical solution, the titanium nitride powder is a composite titanium nitride powder; The raw materials of the composite titanium nitride powder include titanium nitride and polydimethylsiloxane.

[0012] In the present invention, using the composite titanium nitride powder instead of the titanium nitride powder improves the hydrophobicity of the high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane.

[0013] As a further technical solution, the mass ratio of titanium nitride to polydimethylsiloxane is 15:1 - 2.

[0014] In the present invention, by adjusting the mass ratio of titanium nitride to polydimethylsiloxane to 15:1 - 2, the hydrophobicity of the high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane is further improved.

[0015] As a further technical solution, the preparation method of the composite titanium nitride powder is: mixing titanium nitride, titanate coupling agent, and polydimethylsiloxane, ball milling, and heat treatment to obtain the composite titanium nitride powder; The mass ratio of titanium nitride to titanate coupling agent is 30 - 40:1.

[0016] As a further technical solution, the type of the titanate coupling agent includes one of TC-114 and TC-138S; During ball milling, the rotation speed is 300 - 500 rpm and the time is 1 - 2 h.

[0017] As a further technical solution, the particle size of the titanium nitride is 15 - 45 μm.

[0018] As a further technical solution, the temperature of the heat treatment is 400 - 600 °C and the time is 1 - 2 h.

[0019] The present invention also provides a method for preparing the high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane, comprising the following steps: S1. Mix the titanium alloy powder and the titanium nitride powder to obtain a mixture. S2. Design a three-dimensional model of porous titanium and import it into a 3D printer. S3. Layer the mixture using the 3D printer and perform laser sintering in an inert gas atmosphere to obtain the high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane. The inert gas includes one of helium and argon.

[0020] As a further technical solution, the power of the laser sintering is 200 - 500 W, and the scanning speed of the laser sintering is 800 - 1000 mm / s.

[0021] The working principle and beneficial effects of the present invention are as follows: 1. In the present invention, the titanium alloy powder contains manganese and cobalt elements, which synergistically affect the structure of the titanium alloy and synergistically increase the tensile strength of the corrosion-resistant titanium alloy porous hydrophobic membrane.

[0022] 2. In the present invention, titanium nitride powder is added. Titanium nitride has a high melting point and good high-temperature stability. In a high-temperature environment, it can inhibit the grain growth and phase transformation of the titanium alloy matrix and maintain the mechanical properties and structural stability of the material. Specific Embodiments

[0023] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of the present invention.

[0024] In the following embodiments and comparative examples, the particle size of the titanium nitride powder is 20 μm; the model of polydimethylsiloxane is PMX - 200 - 500 cs; the particle size of the titanium nitride is 20 μm.

[0025] Example 1 A high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane is obtained by 3D printing of powders. The powders include titanium alloy powder and titanium nitride powder. The titanium alloy powder is composed of the following elements by weight percentage: aluminum 0.1%, manganese 7.8%, cobalt 5.4%, silicon 0.15%, carbon 0.08%, oxygen 0.1%, nitrogen 0.05%, hydrogen 0.115%, and the balance is titanium; The mass ratio of the titanium alloy powder to the titanium nitride powder is 100:3.7; A method for preparing a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane includes the following steps: S1. Mix the titanium alloy powder and the titanium nitride powder to obtain a mixture; S2. Design a three-dimensional model of porous titanium and import it into a 3D printer; S3. Lay the mixture in layers using a 3D printer and sinter it by laser in an inert gas atmosphere to obtain a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane; The inert gas is helium; The power of the laser sintering is 500 W, and the scanning speed of the laser sintering is 1000 mm / s.

[0026] Example 2 A high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane is obtained by 3D printing of powders. The powders include titanium alloy powder and titanium nitride powder. The titanium alloy powder is composed of the following elements by weight percentage: aluminum 0.03%, manganese 3.5%, cobalt 3.6%, silicon 0.02%, carbon 0.01%, oxygen 0.002%, nitrogen 0.012%, hydrogen 0.003%, and the balance is titanium; The mass ratio of the titanium alloy powder to the titanium nitride powder is 100:2.5; A method for preparing a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane includes the following steps: S1. Mix the titanium alloy powder and the titanium nitride powder to obtain a mixture; S2. Design a three-dimensional model of porous titanium and import it into a 3D printer; S3. Lay the mixture in layers using a 3D printer and sinter it by laser in an inert gas atmosphere to obtain a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane; The inert gas is argon; The power of the laser sintering is 200 W, and the scanning speed of the laser sintering is 800 mm / s.

[0027] Example 3 A high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane is obtained by 3D printing of powders. The powders include titanium alloy powder and titanium nitride powder. The titanium alloy powder is composed of the following elements by weight percentage: aluminum 0.05%, manganese 4.8%, cobalt 5.2%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium; The mass ratio of the titanium alloy powder to the titanium nitride powder is 100:2.9; A method for preparing a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane includes the following steps: S1. Mix the titanium alloy powder and the titanium nitride powder to obtain a mixture; S2. Design a three-dimensional model of porous titanium and import it into a 3D printer; S3. Lay the mixture in layers using a 3D printer and sinter it with a laser in an inert gas atmosphere to obtain a high-strength and corrosion-resistant titanium alloy porous hydrophobic membrane; The inert gas is argon; The power of the laser sintering is 300 W, and the scanning speed of the laser sintering is 900 mm / s.

[0028] Example 4 The difference between this example and Example 3 is only that the titanium alloy powder in this example is composed of the following elements by weight percentage: aluminum 0.05%, manganese 6.2%, cobalt 3.8%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium.

[0029] Example 5 The difference between this example and Example 3 is only that the titanium alloy powder in this example is composed of the following elements by weight percentage: aluminum 0.05%, manganese 5.0%, cobalt 5.0%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium.

[0030] Example 6 The difference between this example and Example 3 is only that the titanium alloy powder in this example is composed of the following elements by weight percentage: aluminum 0.05%, manganese 6.0%, cobalt 4.0%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium.

[0031] Example 7 The difference between this example and Example 6 is only that the titanium nitride powder in this example is replaced with an equal amount of composite titanium nitride powder; The preparation method of the composite titanium nitride powder is: mix titanium nitride, titanate coupling agent, and polydimethylsiloxane, ball mill, and perform heat treatment to obtain the composite titanium nitride powder; The mass ratio of titanium nitride to the titanate coupling agent is 40:1; The mass ratio of titanium nitride to polydimethylsiloxane is 15:3; The type of titanate coupling agent is TC-114; During ball milling, the rotation speed is 500 rpm and the time is 1 h; The temperature of heat treatment is 600 °C and the time is 1 h.

[0032] Example 8 The difference between this example and Example 7 is only that the mass ratio of titanium nitride to polydimethylsiloxane in this example is 30:1.

[0033] Example 9 The difference between this example and Example 7 is only that the mass ratio of titanium nitride to polydimethylsiloxane in this example is 15:1.

[0034] Example 10 The difference between this example and Example 7 is only that the mass ratio of titanium nitride to polydimethylsiloxane in this example is 15:2.

[0035] Example 11 The difference between this example and Example 6 is only that the titanium nitride powder in this example is replaced with an equal amount of composite titanium nitride powder; The preparation method of the composite titanium nitride powder is: mix titanium nitride, titanate coupling agent, and polydimethylsiloxane, ball mill, and heat treat to obtain the composite titanium nitride powder; The mass ratio of titanium nitride to titanate coupling agent is 30:1; The mass ratio of titanium nitride to polydimethylsiloxane is 15:3; The type of titanate coupling agent is TC-138S; During ball milling, the rotation speed is 300 rpm and the time is 2 h; The temperature of heat treatment is 400 °C and the time is 2 h.

[0036] Comparative Example 1 The difference between this comparative example and Example 3 is only that the titanium alloy powder in this comparative example is composed of the following elements by weight percentage: aluminum 0.05%, manganese 10.0%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium.

[0037] Comparative Example 2 The difference between this comparative example and Example 3 is only that the titanium alloy powder in this comparative example is composed of the following elements by weight percentage: aluminum 0.05%, cobalt 10.0%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium.

[0038] Comparative Example 3 The difference between this comparative example and Example 3 is only that the titanium alloy powder in this comparative example is composed of the following elements by weight percentage: aluminum 0.05%, silicon 0.09%, carbon 0.06%, oxygen 0.06%, nitrogen 0.02%, hydrogen 0.01%, and the balance is titanium.

[0039] Experimental Example 1 The high-strength corrosion-resistant titanium alloy porous hydrophobic membranes prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured for tensile strength at 20 °C according to the method specified in GB / T 228.1-2021 "Metallic materials - Tensile testing - Part 1: Method of test at room temperature", and the test results are shown in Table 1.

[0040]

[0041] As can be seen from Table 1, the tensile strength of the high-strength corrosion-resistant titanium alloy porous hydrophobic membranes prepared in Examples 1 to 6 is as high as over 759 MPa, indicating that manganese element and cobalt element have a synergistic effect, improving the tensile strength of the high-strength corrosion-resistant titanium alloy porous hydrophobic membranes.

[0042] Experimental Example 2 The high-strength corrosion-resistant titanium alloy porous hydrophobic membranes prepared in Examples 6 to 11 were tested for water permeation pressure according to the method specified in GB / T 42270-2022 "Test method for hydrophobic properties of porous hydrophobic membranes", and the test results are shown in Table 2.

[0043]

[0044] As can be seen from Table 2, the water permeation pressure of the high-strength corrosion-resistant titanium alloy porous hydrophobic membranes prepared in Examples 7 to 11 is higher than that of Example 6, indicating that using composite titanium nitride powder instead of titanium nitride powder improves the hydrophobicity of the high-strength corrosion-resistant titanium alloy porous hydrophobic membranes.

[0045] Experimental Example 3 The high-strength corrosion-resistant titanium alloy porous hydrophobic membrane prepared in Example 1 was measured for yield strength at 20 °C according to the method specified in GB / T 228.1-2021 "Metallic materials - Tensile testing - Part 1: Method of test at room temperature", and the test results are shown in Table 3.

[0046]

[0047] The test results show that the high-strength corrosion-resistant titanium alloy porous hydrophobic membrane in the present invention can meet the actual use requirements.

[0048] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane, characterized in that: The powder is obtained by 3D printing, wherein the powder includes titanium alloy powder and titanium nitride powder, wherein the titanium alloy powder is composed of the following elements in weight percentage: 0.03% to 0.1% aluminum, 3.5% to 7.8% manganese, 3.6% to 5.4% cobalt, 0.02% to 0.15% silicon, 0.01% to 0.08% carbon, 0.002% to 0.1% oxygen, 0.012% to 0.05% nitrogen, 0.003% to 0.115% hydrogen, and the balance is titanium; The mass ratio of the titanium alloy powder to the titanium nitride powder is 100:2.5-3.

7.

2. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 1, characterized in that: The mass ratio of manganese to cobalt is 1-1.5:

1.

3. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 1, characterized in that: The titanium nitride powder is a composite titanium nitride powder; The raw materials of the composite titanium nitride powder include titanium nitride and polydimethylsiloxane.

4. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 3, characterized in that: The mass ratio of titanium nitride to polydimethylsiloxane is 15:1-2.

5. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 3, characterized in that: The preparation method of the composite titanium nitride powder is as follows: titanium nitride, a titanate coupling agent, and polydimethylsiloxane are mixed, ball-milled, and heat-treated to obtain the composite titanium nitride powder; The mass ratio of the titanium nitride to the titanate coupling agent is 30-40:

1.

6. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 5, characterized in that: The titanate coupling agent includes one of TC-114 and TC-138S; During the ball milling, the rotation speed is 300-500 rpm and the time is 1-2 hours.

7. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 5, characterized in that: The particle size of the titanium nitride is 15-45 μm.

8. The high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 5, characterized in that: The heat treatment temperature is 400-600° C. and the time is 1-2 hours.

9. The method for preparing a high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1, mixing titanium alloy powder and titanium nitride powder to obtain a mixture; S2, design the porous titanium three-dimensional model and import it into the 3D printer; S3, laying the mixture in layers using the 3D printer, and laser sintering under an inert gas atmosphere to obtain a high-strength, corrosion-resistant, titanium alloy porous hydrophobic membrane; The inert gas includes one of helium and argon.

10. The method for preparing a high-strength, corrosion-resistant titanium alloy porous hydrophobic membrane according to claim 9, characterized in that: The power of the laser sintering is 200-500W, and the scanning speed of the laser sintering is 800-1000mm / s.

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