High-density tungsten alloy powder for 3D printing and preparation method thereof

Abstract

The invention discloses high-density tungsten alloy powder for 3D printing. The high-density tungsten alloy powder comprises the following raw materials in parts by weight: 50-55 parts of tungsten powder, 7-11 parts of modified titanium powder, 3-5 parts of cobalt powder, 2-3 parts of nickel powder, 2-4 parts of a cerium-lanthanum additive, 4-7 parts of polyethylene glycol 20000 and 10-15 parts of water. According to the tungsten alloy powder, the tungsten powder serves as a matrix, the modified titanium powder, the cobalt powder, the nickel powder and the cerium-lanthanum additive are added, and through blending, coordination and mutual cooperation improvement of the raw materials, the obtained tungsten alloy powder is excellent in tensile strength and density performance coordination.

Description

Technical Field

[0001] This invention relates to the field of tungsten alloy technology, and more specifically to a high-density tungsten alloy powder for 3D printing and its preparation method. Background Technology

[0002] Tungsten and tungsten alloys possess a series of excellent characteristics, including high density, high hardness, low coefficient of thermal expansion, good corrosion resistance, and thermionic emission capability. In the aerospace field, they can be used to manufacture engine parts and spacecraft structural components; in the defense industry, they can be used to produce armor-piercing projectiles and shielding components; and in the medical field, they can be used to manufacture dental implants and collimators for radiotherapy equipment.

[0003] In order to optimize the tensile strength of existing tungsten alloy powders used for 3D printing, the density of the product is easily reduced, resulting in poor performance coordination and limiting the efficiency of the product. Based on this, the present invention further improves the product. Summary of the Invention

[0004] In view of the deficiencies of the prior art, the purpose of this invention is to provide a high-density tungsten alloy powder for 3D printing and a method for preparing the same, so as to solve the problems mentioned in the background art.

[0005] The present invention solves the technical problem by adopting the following technical solution: This invention provides a high-density tungsten alloy powder for 3D printing, comprising the following parts by weight of raw materials: 50-55 parts tungsten powder, 7-11 parts modified titanium powder, 3-5 parts cobalt powder, 2-3 parts nickel powder, 2-4 parts cerium-lanthanum additive, 4-7 parts polyethylene glycol 20000, and 10-15 parts water.

[0006] Preferably, the specific modification method of the modified titanium powder is as follows: S1: 2-5 parts of niobium powder, 1-3 parts of modified yttrium oxide and 2-3 parts of boron powder are blended and sintered. After sintering, niobium sintering agent is obtained. S2: Titanium powder is first placed in a sodium dodecylbenzenesulfonate solution at a ratio of 3-5 times the total amount of titanium powder, and then 5-8% of niobium sintering agent is added. The mixture is then ball-milled to obtain modified titanium powder.

[0007] Preferably, the sintering temperature of the blending sintering treatment is 300-350℃, and the sintering time is 1 hour.

[0008] Preferably, the sodium dodecylbenzenesulfonate solution has a mass fraction of 5-8%; the ball milling speed for the blending ball milling treatment is 1000-1500 r / min, and the ball milling time is 2 h.

[0009] Preferably, the modified yttrium oxide is prepared by: S1: Heat the graphene at 200-220℃ for 10-20 min, then cool it to 60℃ at a rate of 2-5℃ / min and hold it at that temperature. S2: Mix 3-5 parts of graphene from S1, 5-8 parts of sodium lignosulfonate solution, and 1-3 parts of dopamine hydrochloride solution evenly to obtain graphene solution. Yttrium oxide and graphene solution were ultrasonically treated at a weight ratio of 3:5. After ultrasonication, the mixture was filtered and dried to obtain modified yttrium oxide.

[0010] Preferably, the sodium lignosulfonate solution has a mass fraction of 5-8%; and the dopamine hydrochloride solution has a mass fraction of 2-5%.

[0011] Preferably, the ultrasonic power of the ultrasonic treatment is 350-400W, and the ultrasonic treatment lasts for 1 hour.

[0012] Preferably, the preparation method of the cerium-lanthanum additive is as follows: S11: Irradiate cerium oxide in a proton irradiation chamber for 1 hour with an irradiation power of 350-400W. After irradiation, irradiated cerium oxide is obtained. S12: Irradiated cerium oxide and a 5% lanthanum nitrate solution were stirred evenly at a weight ratio of 2:5, then filtered and dried to obtain the cerium-lanthanum additive.

[0013] The present invention also provides a method for preparing high-density tungsten alloy powder for 3D printing, comprising the following steps: weighing raw materials according to the weight parts, then mixing the raw materials to form a slurry, then spray drying the slurry at a frequency of 60 Hz, and finally sintering to obtain high-density tungsten alloy powder.

[0014] Preferably, the sintering temperature of the sintering treatment is 800-820℃, and the sintering time is 1 hour.

[0015] Compared with the prior art, the present invention has the following beneficial effects: This invention relates to a tungsten alloy powder based on tungsten powder. Modified titanium powder, cobalt powder, nickel powder, and cerium-lanthanum additives are added, and through the harmonization and synergistic effect of these raw materials, the resulting tungsten alloy powder exhibits excellent coordination of tensile strength and density properties. Titanium powder is further optimized by dispersion with sodium dodecylbenzene sulfonate solution, followed by ball milling with a niobium sintering agent. The niobium sintering agent, containing niobium powder, modified yttrium oxide, and boron powder, is further optimized through blending and synergistic effects. Simultaneously, the added modified yttrium oxide undergoes ultrasonic treatment with graphene solution, followed by thermal modification of the graphene. This modified yttrium oxide is then harmonized with sodium lignosulfonate solution and dopamine hydrochloride solution, resulting in a modified yttrium oxide that enhances the system's performance coordination and stability. Finally, the cerium oxide in the cerium-lanthanum additive is activated by proton irradiation and then harmonized with lanthanum nitrate solution, resulting in a superior synergistic effect between the cerium-lanthanum additive and the modified titanium powder, further improving the product's performance. Detailed Implementation

[0016] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] This embodiment of a high-density tungsten alloy powder for 3D printing comprises the following parts by weight of raw materials: 50-55 parts tungsten powder, 7-11 parts modified titanium powder, 3-5 parts cobalt powder, 2-3 parts nickel powder, 2-4 parts cerium-lanthanum additive, 4-7 parts polyethylene glycol 20000, and 10-15 parts water.

[0018] The specific modification method of the modified titanium powder in this embodiment is as follows: S1: 2-5 parts of niobium powder, 1-3 parts of modified yttrium oxide and 2-3 parts of boron powder are blended and sintered. After sintering, niobium sintering agent is obtained. S2: Titanium powder is first placed in a sodium dodecylbenzenesulfonate solution at a ratio of 3-5 times the total amount of titanium powder, and then 5-8% of niobium sintering agent is added. The mixture is then ball-milled to obtain modified titanium powder.

[0019] In this embodiment, the sintering temperature for the blending sintering treatment is 300-350℃, and the sintering time is 1 hour.

[0020] In this embodiment, the sodium dodecylbenzenesulfonate solution has a mass fraction of 5-8%; the ball milling speed for the blending ball milling treatment is 1000-1500 r / min, and the ball milling time is 2 h.

[0021] The method for preparing the modified yttrium oxide in this embodiment is as follows: S1: Heat the graphene at 200-220℃ for 10-20 min, then cool it to 60℃ at a rate of 2-5℃ / min and hold it at that temperature. S2: Mix 3-5 parts of graphene from S1, 5-8 parts of sodium lignosulfonate solution, and 1-3 parts of dopamine hydrochloride solution evenly to obtain graphene solution. Yttrium oxide and graphene solution were ultrasonically treated at a weight ratio of 3:5. After ultrasonication, the mixture was filtered and dried to obtain modified yttrium oxide.

[0022] In this embodiment, the sodium lignosulfonate solution has a mass fraction of 5-8%; the dopamine hydrochloride solution has a mass fraction of 2-5%.

[0023] In this embodiment, the ultrasonic power for ultrasonic treatment is 350-400W, and the ultrasonic treatment lasts for 1 hour.

[0024] The preparation method of the cerium-lanthanum additive in this embodiment is as follows: S11: Irradiate cerium oxide in a proton irradiation chamber for 1 hour with an irradiation power of 350-400W. After irradiation, irradiated cerium oxide is obtained. S12: Irradiated cerium oxide and a 5% lanthanum nitrate solution were stirred evenly at a weight ratio of 2:5, then filtered and dried to obtain the cerium-lanthanum additive.

[0025] This embodiment describes a method for preparing high-density tungsten alloy powder for 3D printing, comprising the following steps: weighing raw materials according to weight parts, mixing the raw materials to form a slurry, spray drying the slurry at an atomizer frequency of 60 Hz, and finally sintering to obtain high-density tungsten alloy powder.

[0026] In this embodiment, the sintering temperature is 800-820℃, and the sintering time is 1 hour.

[0027] Example 1. This embodiment of a high-density tungsten alloy powder for 3D printing comprises the following parts by weight of raw materials: 50 parts tungsten powder, 7 parts modified titanium powder, 3 parts cobalt powder, 2 parts nickel powder, 2 parts cerium-lanthanum additive, 4 parts polyethylene glycol 20000 and 10 parts water.

[0028] The specific modification method of the modified titanium powder in this embodiment is as follows: S1: Two parts of niobium powder, one part of modified yttrium oxide, and two parts of boron powder are blended and sintered. After sintering, niobium sintering agent is obtained. S2: Titanium powder is first placed in a sodium dodecylbenzenesulfonate solution with a total amount of titanium powder of 3 times, and then niobium sintering agent of 5% of the total amount of titanium powder is added. The mixture is then ball-milled to obtain modified titanium powder.

[0029] In this embodiment, the sintering temperature for the blending sintering process is 300°C, and the sintering time is 1 hour.

[0030] In this embodiment, the sodium dodecylbenzenesulfonate solution has a mass fraction of 5%; the ball milling speed for the blending ball milling treatment is 1000 r / min, and the ball milling time is 2 h.

[0031] The method for preparing the modified yttrium oxide in this embodiment is as follows: S1: Heat the graphene at 200°C for 10 min, then cool it to 60°C at a rate of 2°C / min and hold it at that temperature. S2: Mix 3 parts of graphene from S1, 5 parts of sodium lignosulfonate solution, and 1 part of dopamine hydrochloride solution evenly to obtain graphene solution. Yttrium oxide and graphene solution were ultrasonically treated at a weight ratio of 3:5. After ultrasonication, the mixture was filtered and dried to obtain modified yttrium oxide.

[0032] In this embodiment, the sodium lignosulfonate solution has a mass fraction of 5%; the dopamine hydrochloride solution has a mass fraction of 2%.

[0033] In this embodiment, the ultrasonic power for ultrasonic treatment is 350W, and the ultrasonic treatment lasts for 1 hour.

[0034] The preparation method of the cerium-lanthanum additive in this embodiment is as follows: S11: Irradiate cerium oxide in a proton irradiation chamber for 1 hour at a power of 350W. After irradiation, irradiated cerium oxide is obtained. S12: Irradiated cerium oxide and a 5% lanthanum nitrate solution were stirred evenly at a weight ratio of 2:5, then filtered and dried to obtain the cerium-lanthanum additive.

[0035] This embodiment describes a method for preparing high-density tungsten alloy powder for 3D printing, comprising the following steps: weighing raw materials according to weight parts, mixing the raw materials to form a slurry, spray drying the slurry at an atomizer frequency of 60 Hz, and finally sintering to obtain high-density tungsten alloy powder.

[0036] In this embodiment, the sintering temperature is 800℃ and the sintering time is 1 hour.

[0037] Example 2. This embodiment of a high-density tungsten alloy powder for 3D printing comprises the following parts by weight of raw materials: 55 parts tungsten powder, 11 parts modified titanium powder, 5 parts cobalt powder, 3 parts nickel powder, 4 parts cerium-lanthanum additive, 7 parts polyethylene glycol 20000 and 15 parts water.

[0038] The specific modification method of the modified titanium powder in this embodiment is as follows: S1: 5 parts niobium powder, 3 parts modified yttrium oxide and 3 parts boron powder are blended and sintered. After sintering, niobium sintering agent is obtained. S2: Titanium powder is first placed in a sodium dodecylbenzenesulfonate solution with a volume of 5 times the total amount of titanium powder, and then 8% of the total amount of titanium powder as niobium sintering agent is added. The mixture is then ball-milled to obtain modified titanium powder.

[0039] In this embodiment, the sintering temperature for the blending sintering process is 350°C, and the sintering time is 1 hour.

[0040] In this embodiment, the sodium dodecylbenzenesulfonate solution has a mass fraction of 8%; the ball milling speed for the blending ball milling treatment is 1500 r / min, and the ball milling time is 2 h.

[0041] The method for preparing the modified yttrium oxide in this embodiment is as follows: S1: Heat-treat the graphene at 220℃ for 20 minutes, then cool it to 60℃ at a rate of 5℃ / min and hold it at that temperature. S2: Mix 5 parts of graphene from S1, 8 parts of sodium lignosulfonate solution, and 3 parts of dopamine hydrochloride solution evenly to obtain graphene solution. Yttrium oxide and graphene solution were ultrasonically treated at a weight ratio of 3:5. After ultrasonication, the mixture was filtered and dried to obtain modified yttrium oxide.

[0042] In this embodiment, the sodium lignosulfonate solution has a mass fraction of 8%; the dopamine hydrochloride solution has a mass fraction of 5%.

[0043] In this embodiment, the ultrasonic power for ultrasonic treatment is 400W, and the ultrasonic treatment lasts for 1 hour.

[0044] The preparation method of the cerium-lanthanum additive in this embodiment is as follows: S11: Irradiate cerium oxide in a proton irradiation chamber for 1 hour at a power of 400W. After irradiation, irradiated cerium oxide is obtained. S12: Irradiated cerium oxide and a 5% lanthanum nitrate solution were stirred evenly at a weight ratio of 2:5, then filtered and dried to obtain the cerium-lanthanum additive.

[0045] This embodiment describes a method for preparing high-density tungsten alloy powder for 3D printing, comprising the following steps: weighing raw materials according to weight parts, mixing the raw materials to form a slurry, spray drying the slurry at an atomizer frequency of 60 Hz, and finally sintering to obtain high-density tungsten alloy powder.

[0046] In this embodiment, the sintering temperature is 820℃ and the sintering time is 1 hour.

[0047] Example 3. This embodiment of a high-density tungsten alloy powder for 3D printing comprises the following parts by weight of raw materials: The composition includes 52.5 parts tungsten powder, 9 parts modified titanium powder, 4 parts cobalt powder, 2.5 parts nickel powder, 3 parts cerium-lanthanum additive, 5.5 parts polyethylene glycol 20000, and 12.5 parts water.

[0048] The specific modification method of the modified titanium powder in this embodiment is as follows: S1: 3.5 parts of niobium powder, 2 parts of modified yttrium oxide and 2.5 parts of boron powder are blended and sintered. After sintering, niobium sintering agent is obtained. S2: Titanium powder is first placed in a sodium dodecylbenzenesulfonate solution with a total amount of titanium powder of 4 times, and then 6.5% of the total amount of titanium powder of niobium sintering agent is added. The mixture is then ball-milled to obtain modified titanium powder.

[0049] In this embodiment, the sintering temperature for the blending sintering process is 325°C, and the sintering time is 1 hour.

[0050] In this embodiment, the sodium dodecylbenzenesulfonate solution has a mass fraction of 6.5%; the ball milling speed for the blending ball milling treatment is 1250 r / min, and the ball milling time is 2 h.

[0051] The method for preparing the modified yttrium oxide in this embodiment is as follows: S1: Graphene is heat-treated at 210℃ for 15 min, then cooled to 60℃ at a rate of 3.5℃ / min and held at that temperature; S2: Mix 4 parts of graphene from S1, 6.5 parts of sodium lignosulfonate solution, and 2 parts of dopamine hydrochloride solution evenly to obtain graphene solution; Yttrium oxide and graphene solution were ultrasonically treated at a weight ratio of 3:5. After ultrasonication, the mixture was filtered and dried to obtain modified yttrium oxide.

[0052] In this embodiment, the sodium lignosulfonate solution has a mass fraction of 6.5%; the dopamine hydrochloride solution has a mass fraction of 3.5%.

[0053] In this embodiment, the ultrasonic power for ultrasonic treatment is 375W, and the ultrasonic treatment lasts for 1 hour.

[0054] The preparation method of the cerium-lanthanum additive in this embodiment is as follows: S11: Cerium oxide is first irradiated in a proton irradiation chamber for 1 hour at an irradiation power of 375W. After irradiation, irradiated cerium oxide is obtained. S12: Irradiated cerium oxide and a 5% lanthanum nitrate solution were stirred evenly at a weight ratio of 2:5, then filtered and dried to obtain the cerium-lanthanum additive.

[0055] This embodiment describes a method for preparing high-density tungsten alloy powder for 3D printing, comprising the following steps: weighing raw materials according to weight parts, mixing the raw materials to form a slurry, spray drying the slurry at an atomizer frequency of 60 Hz, and finally sintering to obtain high-density tungsten alloy powder.

[0056] In this embodiment, the sintering temperature is 810℃ and the sintering time is 1 hour.

[0057] Comparative Example 1. Unlike Example 3, no modified titanium powder was added.

[0058] Comparative Example 2. Unlike Example 3, no modified yttrium oxide was added to the niobium sintering agent.

[0059] Comparative Example 3. Unlike Example 3, no graphene liquid was added to the modified yttrium oxide.

[0060] Comparative Example 4. Unlike Example 3, no niobium powder and boron powder were added to the niobium sintering agent.

[0061] Comparative Example 5. Unlike Example 3, no cerium-lanthanum additive was added.

[0062] The product performance tests for Examples 1-3 and Comparative Examples 1-5 are as follows:

[0063] As can be seen from Examples 1-3 and Comparative Examples 1-5, the tensile strength and density of the product in Example 3 of the present invention are both excellent; while the performance of the products deteriorates when neither modified titanium powder nor cerium-lanthanum additive is added. Modified titanium powder has the greatest impact on product performance. The performance of the products deteriorates to varying degrees when modified yttrium oxide is not added to the niobium sintering agent, when graphene liquid is not added to the modified yttrium oxide, or when niobium powder and boron powder are not added to the niobium sintering agent. Only when the product raw materials of the present invention are used does the product effect become the most significant.

[0064] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0065] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A high-density tungsten alloy powder for 3D printing, characterized in that, Including the following parts by weight of raw materials: 50-55 parts tungsten powder, 7-11 parts modified titanium powder, 3-5 parts cobalt powder, 2-3 parts nickel powder, 2-4 parts cerium-lanthanum additive, 4-7 parts polyethylene glycol 20000, and 10-15 parts water.

2. The high-density tungsten alloy powder for 3D printing according to claim 1, characterized in that, The specific modification method for the modified titanium powder is as follows: S1: 2-5 parts of niobium powder, 1-3 parts of modified yttrium oxide and 2-3 parts of boron powder are blended and sintered. After sintering, niobium sintering agent is obtained. S2: Titanium powder is first placed in a sodium dodecylbenzenesulfonate solution at a ratio of 3-5 times the total amount of titanium powder, and then 5-8% of niobium sintering agent is added. The mixture is then ball-milled to obtain modified titanium powder.

3. The high-density tungsten alloy powder for 3D printing according to claim 2, characterized in that, The sintering temperature for the blending sintering treatment is 300-350℃, and the sintering time is 1 hour.

4. The high-density tungsten alloy powder for 3D printing according to claim 2, characterized in that, The sodium dodecylbenzenesulfonate solution has a mass fraction of 5-8%; the ball milling speed for the blending ball milling treatment is 1000-1500 r / min, and the ball milling time is 2 h.

5. The high-density tungsten alloy powder for 3D printing according to claim 2, characterized in that, The method for preparing the modified yttrium oxide is as follows: S1: Heat the graphene at 200-220℃ for 10-20 min, then cool it to 60℃ at a rate of 2-5℃ / min and hold it at that temperature. S2: Mix 3-5 parts of graphene from S1, 5-8 parts of sodium lignosulfonate solution, and 1-3 parts of dopamine hydrochloride solution evenly to obtain graphene solution. Yttrium oxide and graphene solution were ultrasonically treated at a weight ratio of 3:

5. After ultrasonication, the mixture was filtered and dried to obtain modified yttrium oxide.

6. The high-density tungsten alloy powder for 3D printing according to claim 5, characterized in that, The sodium lignosulfonate solution has a mass fraction of 5-8%; the dopamine hydrochloride solution has a mass fraction of 2-5%.

7. The high-density tungsten alloy powder for 3D printing according to claim 5, characterized in that, The ultrasonic power of the ultrasonic treatment is 350-400W, and the ultrasonic treatment lasts for 1 hour.

8. The high-density tungsten alloy powder for 3D printing according to claim 5, characterized in that, The preparation method of the cerium-lanthanum additive is as follows: S11: Irradiate cerium oxide in a proton irradiation chamber for 1 hour with an irradiation power of 350-400W. After irradiation, irradiated cerium oxide is obtained. S12: Irradiated cerium oxide and a 5% lanthanum nitrate solution were stirred evenly at a weight ratio of 2:5, then filtered and dried to obtain the cerium-lanthanum additive.

9. A method for preparing high-density tungsten alloy powder for 3D printing as described in any one of claims 1-8, characterized in that, The process includes the following steps: weighing the raw materials according to their weight proportions, mixing the raw materials to form a slurry, spray drying the slurry at a frequency of 60 Hz, and finally sintering to obtain high-density tungsten alloy powder.

10. The method for preparing high-density tungsten alloy powder for 3D printing according to claim 9, characterized in that, The sintering temperature for the sintering treatment is 800-820℃, and the sintering time is 1 hour.

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