A method for preparing titanium-based composite material with enhanced high-temperature hardness

Abstract

The present invention belongs to the technical field of titanium-based composite materials, and specifically discloses a method for preparing a titanium-based composite material with enhanced high-temperature hardness. The method specifically comprises the following steps: preparing eutectic ceramic powder, preparing eutectic ceramic-reinforced titanium-based composite material, and laser 3D printing of the composite material. The present invention prints the eutectic ceramic composite material into metal parts, and the mechanical properties of the metal parts at room temperature and high temperature are significantly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of titanium-based composite materials, and particularly relates to a method for preparing a titanium-based composite material with enhanced high-temperature hardness. Background Art

[0002] Ti6Al4V alloy is an important material for manufacturing high-performance components, widely used in aerospace, marine equipment, and other fields. With the continuous development of the industry, the requirements for the shape complexity and high-temperature resistance of Ti6Al4V components are becoming increasingly higher. The development of processing methods for complex Ti6Al4V components with excellent high-temperature performance is of great significance.

[0003] Selective laser melting (SLM) is a major approach in additive manufacturing of metal materials. Using a laser as its energy source, it scans a bed of metal powder layer by layer, following a path mapped in a 3D CAD slice model. The scanned metal powder melts and solidifies, achieving a metallurgical bond and ultimately producing the metal part designed in the model. SLM overcomes the manufacturing limitations of traditional technologies and can directly form complex metal parts with excellent mechanical properties.

[0004] Adding ceramic components to Ti6Al4V can improve the high-temperature performance of the material. Laser selective melting (SLM) of ceramic particle-reinforced titanium-based composites is an effective approach for manufacturing complex Ti6Al4V parts with excellent high-temperature performance. However, the addition of ceramic materials such as alumina, due to its high melting point, prevents it from being melted well during laser printing, leading to cracking in the Ti6Al4V during additive manufacturing, ultimately leading to forming failure.

[0005] Therefore, it is very necessary to develop a method for preparing titanium-based composite materials with enhanced high-temperature hardness. Summary of the Invention

[0006] The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a titanium-based composite material with enhanced high-temperature hardness.

[0007] To achieve the above objectives, one of the technical solutions of the present invention is: a method for preparing a titanium-based composite material with enhanced high-temperature hardness, specifically comprising the following steps:

[0008] (1) Preparation of eutectic ceramic powder: The raw materials of the eutectic ceramic powder are placed in a ball mill together with a wet grinding medium, and then dried, ground, and sieved to obtain the eutectic ceramic powder;

[0009] (2) Preparation of eutectic ceramic reinforced titanium-based composite material: adding the eutectic ceramic powder and titanium alloy powder obtained in step (1) into a ball mill mixing device in proportion, fully ball milling, drying, and sieving to obtain eutectic ceramic reinforced titanium-based composite material powder;

[0010] (3) Laser 3D printing of composite materials: The eutectic obtained in step (3) is subjected to laser 3D printing. The laser additive manufacturing process adopted in the present invention is selective laser melting. Before printing, the substrate temperature is preheated to 180-220°C, the laser power is 180-220W, the scanning rate is 500-700mm / s, the layer thickness is 20-40μm, the scanning spacing is 0.10-0.15mm, and the laser spot diameter is 60-80μm to obtain a titanium-based composite material with enhanced high-temperature hardness.

[0011] In a preferred embodiment of the present invention, the eutectic ceramic powder in step (1) is a mixed powder of Al2O3 and ZrO2, wherein the particle size distribution of the Al2O3 powder is 5-8 μm, and the particle size of the ZrO2 powder is 150-250 nm; the mass ratio of the Al2O3 powder and the ZrO2 powder in the eutectic ceramic powder is (5-7):(3-5).

[0012] In a preferred embodiment of the present invention, the volume ratio of alcohol to deionized water in the wet grinding medium in step (1) is 1:1.

[0013] Furthermore, the alcohol mass fraction is 65-85%.

[0014] Alcohol has good affinity with ceramic materials, but adding pure alcohol as an auxiliary grinding method will easily cause it to burn due to high temperature. Therefore, adding alcohol and water can maintain good affinity and assist in grinding.

[0015] In a preferred embodiment of the present invention, in step (1), the mass ratio of ball milling balls to material is 3-5:1, and vacuum ball milling is performed at a rotation speed of 150-250 rpm. The ball milling is continued for 5 minutes after each working period of 5 minutes, and the eutectic ceramic composite powder is obtained by ball milling for 3-5 hours.

[0016] In a preferred embodiment of the present invention, the drying temperature in step (1) is 70-90° C., and the drying time is 20-28 h.

[0017] In a preferred embodiment of the present invention, in step (2), the mass ratio of the ball milling balls to the materials of the eutectic ceramic powder and the titanium alloy powder is 4-6:1, the ball milling speed is 100-150 rpm, and the ball milling is carried out for 20-28 hours.

[0018] In a preferred embodiment of the present invention, the drying temperature in step (2) is 70-90° C., the drying time is 20-28 h, and the product is sieved with a 180-220 mesh screen.

[0019] In a preferred embodiment of the present invention, the content of eutectic ceramic powder in the eutectic ceramic reinforced titanium-based composite material in step (2) is 0.5 vol%-1.5 vol%.

[0020] In a preferred embodiment of the present invention, the particle size distribution of the eutectic ceramic reinforced titanium-based composite material prepared in step (2) is 20-45 μm.

[0021] In a preferred embodiment of the present invention, the eutectic ceramic reinforced titanium-based composite material prepared in step (2) has a room temperature Vickers hardness of 342.15 MPa and a 800° C. Vickers hardness of 253.52 MPa.

[0022] In a preferred embodiment of the present invention, in step (3), the laser power is 200 W, the scanning speed is 600 m / s, the scanning interval is 0.12 mm, the layer thickness is 30 μm, and the laser spot diameter is 70 μm.

[0023] To achieve the above objectives, the second technical solution of the present invention is: a titanium-based ceramic composite material printed by laser selective melting.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) The method of the present invention can prepare powder suitable for additive manufacturing and explore the optimal process parameters for printing molded samples with the powder;

[0026] (2) The mechanical properties of metal parts printed from eutectic ceramic composite materials using the method of the present invention are significantly improved at both room temperature and high temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A basic flow chart for the production and printing of the eutectic ceramic reinforced titanium-based composite material provided by the present invention;

[0028] Figure 2 Electron microscope images of the eutectic ceramic powder, eutectic ceramic composite powder, Ti6Al4V powder, and eutectic ceramic-reinforced titanium-based composite material in Example 1: (a) alumina powder, (b) zirconia powder, (c) eutectic ceramic powder, (d) Ti6Al4V powder, and (e) eutectic ceramic-reinforced titanium-based composite material;

[0029] Figure 3The hardness curves at various temperatures are for the titanium-based composite material sample reinforced with high temperature hardness and containing 1 vol% eutectic ceramics prepared in Example 1 and the sample without eutectic ceramics. DETAILED DESCRIPTION

[0030] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention is described in more detail below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited to these embodiments. The same reference numerals throughout the text represent the same elements, and similar reference numerals represent similar elements.

[0031] A method for preparing a titanium-based composite material with enhanced high-temperature hardness comprises the following steps:

[0032] (1) Preparation of eutectic ceramic powder: The raw materials of the eutectic ceramic powder are soaked in alcohol and then put into a ball mill for ball milling. After ball milling, the raw materials are dried, ground, and sieved to obtain the eutectic ceramic powder;

[0033] (2) Preparation of eutectic ceramic reinforced titanium-based composite material: adding the eutectic ceramic powder and titanium alloy powder obtained in step (1) into a ball mill mixing device in proportion, fully ball milling, drying, and sieving to obtain eutectic ceramic reinforced titanium-based composite material powder;

[0034] (3) Laser 3D printing of composite materials: The eutectic obtained in step (3) is subjected to laser 3D printing. The laser additive manufacturing process adopted in the present invention is selective laser melting. Before printing, the substrate temperature is preheated to 180-220°C, the laser power is 180-220W, the scanning rate is 500-700mm / s, the layer thickness is 20-40μm, the scanning spacing is 0.10-0.15mm, and the laser spot diameter is 60-80μm to obtain a titanium-based composite material with enhanced high-temperature hardness.

[0035] In the step (1), the eutectic ceramic powder is a mixed powder of Al2O3 and ZrO2, wherein the particle size distribution of the Al2O3 powder is 5-8 μm, and the particle size of the ZrO2 powder is 150-250 nm; the mass ratio of the Al2O3 powder to the ZrO2 powder in the eutectic ceramic powder is (5-7):(3-5).

[0036] The volume ratio of alcohol to deionized water in the wet grinding medium in step (1) is 1:1.

[0037] The alcohol mass fraction in the step (1) is 65-85%.

[0038] In the step (1), a planetary ball mill is used for the ball milling process, the mass ratio of ball milling balls to materials is 3-5:1, vacuum ball milling is performed at a rotation speed of 150-250 rpm, and the ball milling is continued for 5 minutes after each working period. The eutectic ceramic composite powder is obtained by ball milling for 3-5 hours.

[0039] In the step (1), the drying temperature is 70-90° C. and the drying time is 20-28 hours.

[0040] In the step (2), the mass ratio of the ball milling balls of the eutectic ceramic powder and the titanium alloy powder to the material is 4-6:1, the ball milling speed is 100-150 rpm, the ball milling is performed for 20-28 hours, and the powder is dried at 70-90° C., and then sieved with a 180-220 mesh screen.

[0041] In the step (2), the drying temperature is 70-90° C. and the drying time is 20-28 hours.

[0042] The content of eutectic ceramic powder in the eutectic ceramic reinforced titanium-based composite material in step (2) is 0.5-1.5 vol%.

[0043] The eutectic ceramic reinforced titanium-based composite material prepared in step (2) has a particle size distribution of 20-45 μm.

[0044] The eutectic ceramic reinforced titanium-based composite material prepared in the step (2) has a room temperature Vickers hardness of 342.15 MPa and a 800° C. Vickers hardness of 253.52 MPa.

[0045] In the step (3), the laser power is 200 W, the scanning speed is 600 m / s, the scanning interval is 0.12 mm, the layer thickness is 30 μm, and the laser spot diameter is 70 μm.

[0046] A eutectic ceramic reinforced titanium matrix composite metal sample printed by selective laser melting.

[0047] Example 1

[0048] A titanium-based composite material with enhanced high-temperature hardness is prepared by the following method:

[0049] (1) Preparation of eutectic ceramic powder: The mass ratio of alumina to zirconia in the eutectic ceramic powder is 57.5:42.5. Under this condition, the melting point of alumina can be reduced from 2313K to 2133K, so that alumina can be melted better, and the oxide eutectic ceramic powder can effectively suppress cracks caused by the process; the eutectic ceramic powders of alumina and zirconia are put into a drum for ball milling, the ball-to-material ratio is 4:1, the ball milling speed is 200 rpm, the ball milling time is 4 hours, and the ball milling is continued after every 5 minutes of work and 5 minutes of rest; the mixed powder after ball milling is dried at a drying temperature of 80°C to dry out all moisture and then agglomerate; after grinding, it is sieved with a 100-mesh sieve to obtain the eutectic ceramic powder;

[0050] (2) Preparation of eutectic ceramic reinforced titanium-based composite material: a ceramic reinforced Ti6Al4V composite powder containing 1 vol% of eutectic ceramic powder was prepared, with a ball-to-material ratio of 4:1 and a ball milling speed of 120 rpm. The milling was continued for 24 h, and then dried at a drying temperature of 80°C for 24 h to obtain a eutectic ceramic reinforced titanium-based composite material; wherein 200 ml contained 198 ml of Tl6Al4V and 2 ml of Al2O3-ZrO2, the mass of 198 ml of Tl6Al4V was approximately 481.58 g, and the mass of 2 ml of Al2O3-ZrO2 was approximately 1.18 g; the powder particle size of the obtained eutectic ceramic reinforced titanium-based composite material was tested by a particle size analyzer, and the results showed that the powder particle size distribution was 20-45 μm;

[0051] (3) Laser 3D printing of composite materials: 30 rectangular blocks with different input parameters and dimensions of 10 mm × 10 mm × 12 mm were created on a 125 mm × 125 mm substrate for parameter verification and printing. The 30 samples were numbered, and the layer thickness (H) of samples 1 to 30 was 30 μm. The scanning spacing (D) of samples 1 to 15 was 0.12 mm, and the scanning spacing (D) of samples 16 to 30 was 0.1 mm. The laser power (P) was increased from 150 W to 50 W. The laser power was increased by 300 s / mm to 350 W; the scanning speed (V) was increased from 600 s / mm to 1200 s / mm; the laser power and the scanning speed were increased synchronously; the 1 vol% eutectic ceramic composite powder in step 2 was laser 3D printed using the above-set parameters. Since the mixed powder contained eutectic ceramic particles, in order to increase the stability of the sample on the substrate, the first layer was printed twice, and finally the titanium-based composite material with enhanced high-temperature hardness was selected with the best forming effect.

[0052] refer to Figure 2, where (a) is an electron microscope image of Al2O3 powder, (b) is an electron microscope image of ZrO2 powder, (c) is an electron microscope image of titanium alloy powder, (d) is an electron microscope image of eutectic ceramic composite powder, and (e) is an electron microscope image of eutectic ceramic reinforced titanium-based composite powder. Figure 2 (e) It can be seen that the eutectic ceramic composite powder particles are uniformly attached to the surface of the titanium alloy powder; the powder particle size of the composite powder is detected by a particle size analyzer, and the results show that the particle size distribution of the composite powder is 20-45 μm.

[0053] The obtained high-temperature hardness-enhanced titanium-based composite material samples were tested for room temperature and high temperature hardness properties using iVickyV2.0 Vickers hardness tester and HTV-PHS30 high-temperature Vickers hardness tester respectively. Figure 3 The hardness curves at various temperatures for the titanium-based composite material sample reinforced with high temperature hardness and containing 1 vol% eutectic ceramics and the sample without eutectic ceramics prepared in Example 1 are shown in FIG. Figure 3 The room-temperature hardness of the selected samples was measured using an iVicky V2.0 Vickers hardness tester. The results showed that the room-temperature hardness of the selected samples reached 342.15 MPa when the eutectic ceramic particle content was 1 vol%, and 330.94 MPa when it was 0 vol%. The high-temperature hardness of the samples at 800°C was measured using an HTV-PHS30 high-temperature Vickers hardness tester. The results showed that the high-temperature hardness of the samples reached 253.52 MPa when the eutectic ceramic content was 1 vol%, and 220.59 MPa when it was 0 vol%.

[0054] Example 2

[0055] The high-temperature-resistant, high-hardness composite powder obtained in Example 1 was fed into an SLM printer for laser 3D printing. Laser 3D printing process parameters: 30 rectangular blocks measuring 10 mm × 10 mm × 12 mm with different input parameters were created on a 125 mm × 125 mm × 125 mm substrate for parameter verification printing. For the 30 samples, the powder layer thickness (H) for samples 1-30 was 30 μm. The scanning distance (D) for samples 1-15 was 0.12 mm, and the scanning distance (D) for samples 16-30 was 0.1 mm. The laser power (P) was set from 150 W in increments of 50 W to 350 W. The scanning speed (V) was increased from 600 s / mm in increments of 300 s / mm to 1200 s / mm. The laser power and scanning speed were increased simultaneously. The substrate preheat temperature was 200°C, and the laser spot diameter was 70 μm. Since the mixed powder contains eutectic ceramic particles, in order to increase the stability of the sample on the substrate, the first layer is set to be printed twice.

[0056] After printing, the room temperature hardness of the selected samples was measured using an iVickyV2.0 Vickers hardness tester. The results showed that the composite material powder had the best effect after 3D printing when the laser power was 150W, the scanning rate was 900mm / s, the scanning spacing was 0.1mm, the layer thickness was 30μm, and the laser spot diameter was 70μm. When the eutectic ceramic particle content was 1vol% at room temperature, it could reach 353.51HV, and when it was 0vol%, it was only 330.94MPa. The high temperature hardness of the sample at 800℃ was measured using an HTV-PHS30 high temperature Vickers hardness tester. The results showed that when the eutectic ceramic content was 1vol%, it could reach 271.55MPa, and when it was 0vol%, it could reach 220.59MPa.

[0057] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein with equivalents. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a titanium-based composite material with enhanced high-temperature hardness, characterized in that: The following steps are involved: (1) Preparation of eutectic ceramic powder: The raw materials of eutectic ceramic powder are placed in a ball mill together with a wet grinding medium. After ball milling, the eutectic ceramic powder is dried, ground, and sieved to obtain the eutectic ceramic powder. The eutectic ceramic powder is a mixed powder of Al2O3 and ZrO2, and the mass ratio of Al2O3 powder to ZrO2 powder is (5-7): (3-5). (2) Preparation of eutectic ceramic reinforced titanium-based composite material: the eutectic ceramic powder and titanium alloy powder prepared in step (1) are added into a ball mill mixing device in proportion, fully ball milled, dried, and sieved to obtain eutectic ceramic reinforced titanium-based composite powder; (3) Laser 3D printing of composite materials: The eutectic porcelain reinforced titanium-based composite powder obtained in step (2) was subjected to laser 3D printing, and laser selective melting was used for forming. Before printing, the substrate temperature was preheated to 180-220°C, the laser power was 180-220W, the scanning rate was 500-700mm / s, the layer thickness was 20-40μm, the scanning spacing was 0.10-0.12mm, and the laser spot diameter was 60-80μm to obtain a titanium-based composite material with enhanced high-temperature hardness.

2. The method for preparing the titanium-based composite material according to claim 1, wherein: In the step (1), the eutectic ceramic powder is a mixed powder of Al2O3 and ZrO2, the mass ratio of Al2O3 to ZrO2 is (5-7): (3-5), the particle size of the Al2O3 powder is 5-8 μm, and the particle size of the ZrO2 powder is 150-250 nm.

3. The method for preparing the titanium-based composite material according to claim 1, wherein: In the step (1), the volume ratio of alcohol to deionized water in the wet grinding medium is 1:

1.

4. The method for preparing the titanium-based composite material according to claim 3, wherein: The alcohol mass fraction is 65-85%.

5. The method for preparing the titanium-based composite material according to claim 1, wherein: In the step (1), the mass ratio of ball milling balls to materials is 3-5:1, the rotation speed is 150-250 rpm, and the milling is continued after 5 minutes of work, and the milling time is 3-5 hours.

6. The method for preparing the titanium-based composite material according to claim 1, wherein: In the step (2), the mass ratio of the ball milling balls of the eutectic ceramic powder and the titanium alloy powder to the materials is 4-6:1, the ball milling speed is 100-150 rpm, and the ball milling is carried out for 20-28 hours.

7. The method for preparing the titanium-based composite material according to claim 1, wherein: The content of eutectic ceramic powder in the eutectic ceramic reinforced titanium-based composite material in step (2) is 0.5 vol%-1.5 vol%.

8. The method for preparing the titanium-based composite material according to claim 1, wherein: The eutectic ceramic reinforced titanium-based composite material prepared in step (2) has a particle size distribution of 20-45 μm.

9. The method for preparing the titanium-based composite material according to claim 1, wherein: In step (3), the laser power is 200 W, the scanning speed is 600 m / s, the scanning interval is 0.12 mm, the layer thickness is 30 μm, and the laser spot diameter is 70 μm.

10. A titanium-based ceramic composite material obtained by the method for preparing a titanium-based composite material according to any one of claims 1 to 9.

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