Hard alloy additive powder for additive manufacturing and application thereof
By using cemented carbide additive powder composed of carbide ceramics, metal binders and free carbon in metal additive manufacturing, the problems of uneven distribution and weak bonding of carbides are solved, and the density of additive manufacturing parts is improved , hardness and wear resistance meet the application requirements of high performance requirements.
Patent Information
- Application Number
- CN202411018228.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-26
- Publication Date
- 2024-12-10
AI Technical Summary
During the metal additive manufacturing process, the direct addition of carbide powder causes uneven distribution of carbides in the molded parts, poor flow performance, low density, and weak combination of carbides with metal substrates, making it difficult to improve material performance, especially for high strength , places with high requirements for hardness and wear resistance cannot meet the use requirements.
The cemented carbide additive powder consisting of dense spherical particles containing carbide ceramics, metal binders and free carbon was prepared by plasma technology. The proportion of carbide ceramics is 68.0-92.0 wt.%, and the metal binders are The proportion is 5.0-30.0 wt.%, and the proportion of free carbon is 1.0-5.0 wt.%, which is mixed with the raw material spherical metal powder and additive manufacturing is carried out by laser powder bed melting, electron beam powder bed melting and other methods.
It improves the density, hardness, wear resistance and tensile properties of the molded parts, enhances the combination of carbides and metal matrix, ensures the forming quality and performance of the molded parts, and broadens the application range of metal additive manufacturing.
Smart Images
Figure CN119098584A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of additive manufacturing, and in particular to a cemented carbide additive powder for additive manufacturing and application thereof. Background Art
[0002] Metal additive manufacturing technology, also known as metal 3D printing technology, is a manufacturing technology that relies on three-dimensional model data and layer-by-layer material forming. Common metal additive manufacturing technologies include laser powder bed melting, electron beam powder bed melting, and directed energy deposition. This technology has strong customization capabilities and has significant advantages in manufacturing complex structural parts. Whether it is high-performance parts in the aerospace field or customized medical devices in the medical industry, metal additive manufacturing plays a vital role. It not only greatly shortens the product development cycle, but also greatly broadens the possibility of design and manufacturing, bringing revolutionary breakthroughs and development opportunities to the modern manufacturing industry.
[0003] However, compared with traditional manufacturing methods, the performance of some metal additive manufacturing parts is worse than that of parts prepared by traditional manufacturing methods. For some places of use that have high requirements for material strength, hardness and wear resistance, parts made by additive manufacturing cannot meet the requirements. Refractory metal carbides have excellent properties such as high hardness, high strength and high wear resistance. At the same time, relevant studies have shown that adding carbide ceramics to metal materials can play a certain strengthening role. However, directly adding carbide powder in the additive manufacturing process will lead to uneven distribution of carbides in the formed parts, and directly adding carbide powder will cause the flowability and bulk density of the mixed powder to deteriorate, resulting in low density of the formed parts, affecting the performance of the formed parts; in addition, directly adding carbide powder for additive manufacturing often makes it difficult for the carbide to play a reinforcing role due to the weak bonding between carbide ceramics and the metal matrix, and it is easy to fall off during use. Therefore, it is urgent to prepare a spherical cemented carbide powder as an additive in the additive manufacturing process to improve the performance of the formed parts and broaden the application market of metal additive manufacturing. Summary of the invention
[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a cemented carbide additive powder for additive manufacturing and its application, which is mixed with raw spherical metal powder in the additive manufacturing process and then used to adjust the phase composition of the formed part and improve the performance of the additively manufactured formed part.
[0005] The objective of the present invention is achieved through the following measures: A cemented carbide additive powder for additive manufacturing, consisting of dense spherical particles containing carbide ceramics, metal binders and free carbon, wherein the carbide ceramics account for 68.0-92.0wt.%, the metal binder accounts for 5.0-30.0wt.%, and the free carbon accounts for 1.0-5.0wt.%.
[0006] Preferably, in the dense spherical particles, the proportion of carbide ceramics is 80.0wt.%, the proportion of metal binder is 17.0wt.%, and the proportion of free carbon is 3.0wt.%.
[0007] Preferably, the components inside the dense spherical particles are evenly distributed, and the average particle size is 30-60 μm.
[0008] Preferably, the metal binder includes one or more of Fe, Co, Ni, and Ti metals.
[0009] Preferably, the carbide ceramic includes one or more of tungsten carbide, titanium carbide, niobium carbide, and zirconium carbide.
[0010] The above-mentioned method for preparing cemented carbide additive powder for additive manufacturing uses plasma technology to prepare cemented carbide additive powder. The plasma includes microwave plasma, inductively coupled plasma, and direct current plasma. The core zone temperature of the plasma should not be lower than 5000K.
[0011] The application of the cemented carbide additive powder for additive manufacturing is to add the prepared cemented carbide additive powder to titanium alloy, stainless steel, cobalt-chromium alloy, nickel-based high-temperature alloy, magnesium alloy, and aluminum alloy for additive manufacturing.
[0012] In the application of the cemented carbide additive powder for additive manufacturing, the additive raw material is mixed with the cemented carbide additive powder, and the carbide content in the mixed powder should be 0.1-5.0wt.%.
[0013] The above-mentioned application of cemented carbide additive powder for additive manufacturing, the additive manufacturing method includes one of laser powder bed melting, electron beam powder bed melting, and directed energy deposition.
[0014] Beneficial effects of the present invention: A cemented carbide additive powder for additive manufacturing has the advantage that after mixing it with the spherical powder to be additively manufactured, it will not affect the flow properties of the raw material powder, thereby ensuring the forming quality of the formed part. In addition, when it is used as an additive in the additive manufacturing process, the carbide particles can be used as a dispersed reinforcement phase to improve the strength, hardness, wear resistance and other properties of the formed metal material; on the one hand, the metal binder can improve the bonding strength between carbides in the cemented carbide additive powder, and at the same time, during the additive manufacturing process, the type of binder can be changed according to the composition of the matrix, so that it forms an alloy and a solid solution with the matrix to improve the performance of the formed part; free carbon can combine with the additive manufacturing matrix to generate a ceramic phase with higher strength, which increases the boundary layer strength between the additive powder and the matrix. At the same time, during the additive manufacturing process, the free carbon can also penetrate into the matrix to form a higher strength alloy with the matrix. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 Example 1 SEM image of cemented carbide additive powder for additive manufacturing;
[0016] Figure 2 Example 1 SEM-EDS image of the surface of cemented carbide additive powder for additive manufacturing;
[0017] Figure 3 Example 1 XRD pattern of cemented carbide additive powder for additive manufacturing;
[0018] Figure 4 Example 1 SEM image of WC-Co doped H13 tool steel laser powder bed melting sample. DETAILED DESCRIPTION
[0019] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0020] Embodiment 1:
[0021] The H13 tool steel matrix is doped with 3wt.% tungsten carbide powder. The cemented carbide additive powder WC-Co with a tungsten carbide content of 70wt.%, a binder cobalt content of 26.6wt.%, a free carbon content of 3.4wt.%, and an average particle size of 32μm is used. The SEM, EDS and XRD diagrams are shown in the figure. Figure 1, 2, 3. The WC-Co additive and the H13 powder prepared by atomization method were mixed in a mass ratio of 4.3:95.7, and the mixed powder was formed by laser powder bed melting. The formed parts were compared with the parts without additives. The density of the parts without additives was 98.2%, and the density of the formed parts after adding additives was 98.5%. The hardness of the formed parts with cemented carbide additives increased by 37%, the friction coefficient decreased by 13%, and the tensile performance increased by 17%.
[0022] Embodiment 2:
[0023] The H13 tool steel matrix is doped with 3wt.% tungsten carbide powder and 1wt.% zirconium carbide powder. The cemented carbide additive powder WC-ZrC-Fe with a tungsten carbide content of 60wt.%, a zirconium carbide content of 20wt.%, a binder iron content of 16.9wt.%, a free carbon content of 3.1wt.%, and an average particle size of 30μm is used. The WC-ZrC-Fe additive and the H13 powder prepared by atomization method are mixed in a mass ratio of 1:19, and the mixed powder is formed by laser powder bed melting. The formed parts are compared with the parts without additives. The density of the parts without additives is 98.2%, and the density of the formed parts after adding additives is 98.7%. The hardness of the formed parts with the addition of cemented carbide additives is increased by 40%, the friction coefficient is reduced by 20%, and the tensile properties are improved by 21%.
[0024] Embodiment 3:
[0025] Zirconium carbide powder with a mass fraction of 1wt.% is doped on the nickel-based high-temperature alloy GH4169 matrix. Cemented carbide additive powder ZrC-Ni with a zirconium carbide content of 80wt.%, a binder nickel content of 17.8wt.%, a free carbon content of 2.2wt.%, and an average particle size of 34μm is used. The ZrC-Ni additive and the nickel-based high-temperature alloy GH4169 powder prepared by atomization method are mixed in a mass ratio of 1:79, and the mixed powder is formed by laser powder bed melting. The formed parts are compared with the parts without additives. The density of the parts without additives is 97.1%, and the density of the formed parts after adding additives is 97.2%. The hardness of the formed parts with the addition of cemented carbide additives is increased by 19%, the friction coefficient is reduced by 10%, and the tensile properties are increased by 30%.
[0026] Embodiment 4:
[0027] Tungsten carbide powder with a mass fraction of 5wt.% is doped on the cobalt-chromium alloy CoCr01 matrix. Use cemented carbide additive powder WC-Co with a tungsten carbide content of 83wt.%, a binder cobalt content of 12wt.%, a free carbon content of 5.0wt.%, and an average particle size of 32μm. The WC-Co additive and spherical CoCr01 powder are mixed in a mass ratio of 1:16, and the mixed powder is formed by laser powder bed melting. The formed parts are compared with the parts without additives. The density of the parts without additives is 98.7%, and the density of the formed parts after adding additives is 98.7%. The hardness of the formed parts with the addition of cemented carbide additives is increased by 15%, the friction coefficient is reduced by 20%, and the tensile properties are improved by 18%.
[0028] Embodiment 5:
[0029] The titanium alloy TC4 matrix is doped with zirconium carbide powder with a mass fraction of 3wt.%. The zirconium carbide content is 70wt.%, the binder titanium content is 28wt.%, the free carbon content is 3wt.%, and the average particle size is 32μm. The ZrC-Ti additive and the spherical TC4 powder prepared by atomization method are mixed in a mass ratio of 4.3:95.7, and the mixed powder is formed by laser powder bed melting. The formed parts are compared with the parts without additives. The density of the parts without additives is 98.3%, and the density of the formed parts after adding additives is 98.7%. The hardness of the formed parts with the addition of cemented carbide additives is increased by 17%, the friction coefficient is reduced by 21%, and the tensile properties are improved by 23%.
[0030] Embodiment 6: A cemented carbide additive powder for additive manufacturing, composed of dense spherical particles containing carbide ceramics, metal binders and free carbon, wherein the carbide ceramics are titanium carbide, accounting for 80wt.%, the metal binder is iron, accounting for 17.0wt.%, and the free carbon accounts for 3.0wt.%, and the components inside the dense spherical particles are evenly distributed, with an average particle size of 60μm. The cemented carbide additive powder is prepared by plasma technology, the plasma is microwave plasma, and the temperature of the core area of the plasma is not less than 5000K.
[0031] The preparation method of cemented carbide additive powder for additive manufacturing in the above-mentioned embodiments 1-6 uses plasma technology to prepare cemented carbide additive powder, and the plasma includes but is not limited to microwave plasma, inductively coupled plasma, and DC plasma. The core temperature of the plasma should not be lower than 5000K. The application of cemented carbide additive powder for additive manufacturing can be used to perform additive manufacturing on titanium alloys, stainless steel, cobalt-chromium alloys, nickel-based high-temperature alloys, magnesium alloys, and aluminum alloys using the prepared cemented carbide additive powder. The additive raw material is mixed with the cemented carbide additive powder, and the carbide content in the mixed powder is 0.1-5.0wt.%. The additive manufacturing method not only includes laser powder bed melting, but also includes electron beam powder bed melting and directed energy deposition.
[0032] Finally, it should be noted that the above 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, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A cemented carbide additive powder for additive manufacturing, characterized in that: It is composed of dense spherical particles containing carbide ceramics, metal binders and free carbon, wherein the carbide ceramics account for 68.0-92.0wt.%, the metal binder accounts for 5.0-30.0wt.%, and the free carbon accounts for 1.0-5.0wt.%.
2. The cemented carbide additive powder for additive manufacturing according to claim 1, characterized in that: In the dense spherical particles, the proportion of carbide ceramics is 80.0wt.%, the proportion of metal binder is 17.0wt.%, and the proportion of free carbon is 3.0wt.%.
3. The cemented carbide additive powder for additive manufacturing according to claim 2, characterized in that: The components inside the dense spherical particles are evenly distributed, and the average particle size is 30-60 μm.
4. The cemented carbide additive powder for additive manufacturing according to claim 3, characterized in that: The metal binder includes one or more of Fe, Co, Ni and Ti metals.
5. The cemented carbide additive powder for additive manufacturing according to claim 3, characterized in that: The carbide ceramic includes one or more of tungsten carbide, titanium carbide, niobium carbide, and zirconium carbide.
6. A method for preparing cemented carbide additive powder for additive manufacturing as claimed in claim 1, characterized in that: The cemented carbide additive powder is prepared by plasma technology, wherein the plasma includes microwave plasma, inductively coupled plasma, and direct current plasma, and the core temperature of the plasma should be no less than 5000K.
7. A use of the cemented carbide additive powder for additive manufacturing as claimed in claim 1, characterized in that: The prepared cemented carbide additive powder is added to titanium alloy, stainless steel, cobalt-chromium alloy, nickel-based high-temperature alloy, magnesium alloy and aluminum alloy for additive manufacturing.
8. The use of cemented carbide additive powder for additive manufacturing according to claim 7, characterized in that: The additive raw material is mixed with the cemented carbide additive powder, and the carbide content in the mixed powder is 0.1-5.0wt.%.
9. The use of cemented carbide additive powder for additive manufacturing according to claim 8, characterized in that: Additive manufacturing methods include laser powder bed fusion, electron beam powder bed fusion, and directed energy deposition.