CN118123014A - Copper-chromium-niobium composite powder for laser additive manufacturing and preparation method thereof - Google Patents
Copper-chromium-niobium composite powder for laser additive manufacturing and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 97
- CABYUSONEWUEOJ-UHFFFAOYSA-N chromium copper niobium Chemical compound [Cu][Cr][Nb] CABYUSONEWUEOJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 title claims abstract description 24
- 230000000996 additive effect Effects 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 103
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 81
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000011651 chromium Substances 0.000 claims abstract description 66
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 65
- 238000000498 ball milling Methods 0.000 claims abstract description 64
- 239000010949 copper Substances 0.000 claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 claims abstract description 50
- 230000001788 irregular Effects 0.000 claims abstract description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 23
- 229910001257 Nb alloy Inorganic materials 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 229910052786 argon Inorganic materials 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000010955 niobium Substances 0.000 claims description 29
- 229910052758 niobium Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims 2
- 238000002310 reflectometry Methods 0.000 abstract description 7
- 241000207961 Sesamum Species 0.000 abstract description 5
- 235000003434 Sesamum indicum Nutrition 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- QVZNQFNKKMMPFH-UHFFFAOYSA-N chromium niobium Chemical compound [Cr].[Nb] QVZNQFNKKMMPFH-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of copper-chromium-niobium powder for laser additive manufacturing, which comprises the following steps of 1) preparing simple substance powder, and selecting pure copper powder with spherical shape and particle size range of 180-200 mu m; pure chromium and pure niobium powder with particle size of 5-20 μm and irregular shape. Annealing the pure copper powder in a reducing atmosphere, and vacuum drying the pure chromium and pure niobium powder; 2) Under the protection of argon, putting pure copper, pure chromium and pure niobium powder into a ball milling tank for mixing, and performing low-speed ball milling in a planetary ball mill to obtain the copper-chromium-niobium powder. The prepared copper-chromium-niobium powder is spherical copper powder, the surface of which is inlaid with irregular chromium and niobium powder, and the copper-chromium-niobium powder has a special microstructure similar to sesame balls. The copper-chromium-niobium powder with the structure is used for laser additive manufacturing, has good fluidity and low reflectivity to infrared laser, and the copper-chromium-niobium alloy manufactured by the laser additive manufacturing has few defects and good mechanical and electrical properties.
Description
Technical Field
The application relates to the technical field of laser additive manufacturing, in particular to a preparation method of copper-chromium-niobium powder for additive manufacturing of copper-chromium-niobium alloy.
Background
The united states national aerospace agency is currently making full use of additive manufacturing techniques to manufacture rocket propulsion systems to shorten test time and iterations of design-fail-repair cycles. Other advantages of additive manufacturing have been demonstrated on rockets, including a substantial reduction in overall cost and time, integrated fabrication of parts, the ability to shape complex geometries, and improvements in alloy performance with small melt pools and high cooling rates using additive manufacturing. The laser directional energy deposition (L-DED) is a common metal additive manufacturing technology, and has the characteristics of high forming speed, high manufacturing freedom, high processing precision and the like. Compared with the traditional manufacturing process, the L-DED process is used for forming a small number of devices with complex structures, so that the material utilization rate can be improved, the manufacturing period can be shortened, and the method is more suitable for the field of aerospace.
The Cu-Cr-Nb alloy is widely applied to high-temperature service environments such as liquid rocket engines, thermal nuclear reactors and the like due to excellent high-temperature mechanical properties and conductivity. For rocket engine combustors, the use of laser additive manufacturing techniques to manufacture copper-chromium-niobium combustion chamber inner walls is considered to be the most promising technological route. However, when the copper-chromium-niobium alloy powder is used for laser additive manufacturing of the copper-chromium-niobium inner wall, 1. The alloy powder is difficult to prepare, expensive and difficult to obtain; 2. the solid solubility of chromium niobium in copper is low, and the alloy content is difficult to improve; 3. copper-chromium-niobium powder has uneven components, alloy powder adjustment components need to be smelted again for powder preparation, and the cost is high; 4. the technical progress is severely limited by a plurality of difficulties such as low energy absorptivity caused by high infrared laser reflectivity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of copper-chromium-niobium powder which is easy to obtain raw materials, uniform and adjustable in components, high in fluidity and low in infrared laser reflectivity.
The technical scheme provided by the invention is as follows.
The invention prepares copper-chromium-niobium powder by pure copper, pure chromium and pure niobium simple substance powder, which comprises the following steps:
1) Preparing simple substance powder: and (3) respectively weighing pure copper, pure chromium and pure niobium simple substance powder according to the total weight and the components of the required copper-chromium-niobium alloy. Wherein, the grain diameter of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ in a reducing atmosphere, and drying the pure chromium and pure niobium powder in a vacuum drying oven at 100 ℃ for 2 hours.
2) Mixing and ball milling: under the protection of argon, pure copper, pure chromium and pure niobium powder are put into a ball milling tank for mixing, ball milling is carried out at a low speed in a planetary ball mill, the ball milling balls are copper balls with the diameters of 3mm, 6mm and 10mm in the number ratio of 1:1:1, the ball material weight ratio is 4:1 or 6:1, the ball milling rotating speed interval is 100-300rpm, and the ball milling time is 2-4h. And (3) performing low-speed ball milling to obtain the copper-chromium-niobium mixed powder. The powder is copper powder with chromium and niobium powder embedded on the surface, and has a special structure similar to sesame ball shape.
3) And finally, sieving the mixed powder to obtain copper-chromium-niobium powder with proper particle size.
The prepared copper-chromium-niobium powder is used as a raw material for additive manufacturing, and is sent into L-DED equipment to realize additive manufacturing of copper-chromium-niobium alloy.
In order to overcome the problem of high reflection of copper powder to infrared laser, the invention designs a special structure which is formed by embedding chromium and niobium micro powder with irregular shapes on the surface of a copper ball to form a sesame-like ball shape. On one hand, the reflectivity of copper powder to infrared laser is reduced by using chromium and niobium micron powder inlaid on the surface, and on the other hand, the mixing of copper, chromium and niobium is realized by using the sesame ball-like structure, so that the component uniformity of the laser additive copper-chromium-niobium alloy is ensured. In order to realize the sesame ball structure, the invention specially designs spherical copper powder with the particle size range of 180-200 mu m and chromium and niobium powder with the particle size range of 5-20 mu m and irregular shape as raw materials, and the irregular micro powder is inlaid on the surface of the spherical powder by organically matching coarse spherical powder with fine irregular powder. Furthermore, in order to ensure the embedding effect, the invention requires that the pure copper powder is annealed for 4 hours at 500 ℃ so that the pure copper powder is fully annealed and softened to facilitate the embedding of the chromium and niobium irregular micro powder into the surface of the copper ball. In order to avoid severe deformation and flattening of the spherical powder, the invention designs a low-speed ball milling condition and ensures the fluidity of the obtained powder. The high-quality copper-chromium-niobium composite powder is obtained by matching the technical means of powder raw material selection, copper powder annealing, low-speed ball milling and the like, and the purposes of easily obtained raw materials, uniform and adjustable components, high fluidity and low infrared laser reflectivity are realized for additive manufacturing of copper-chromium-niobium alloy.
The invention has the beneficial effects that:
1. The copper, chromium and niobium powder used in the invention are all simple substance powder, so that the method is convenient to obtain; chromium and niobium powder is in an irregular form of mechanical crushing, has low powder requirement, is easy to prepare and has relatively low price.
2. The invention does not add auxiliary agent in the ball milling process, has argon protection atmosphere, and the grinding ball is copper, thereby avoiding introducing other impurities.
3. Under the impact action of the metal copper balls, chromium and niobium powder are inlaid on the surface of the copper powder to form a special structure similar to sesame balls, and the special structure can improve the compactness and uniformity of the copper, chromium and niobium powder, reduce the high laser reflectivity of the copper powder, and is beneficial to preparing metal blocks with few defects and good performance by a laser additive manufacturing technology.
4. Under the low rotation speed of the planetary ball mill, the phenomenon that chromium and niobium powder is embedded into the surface of copper powder is obvious, the cold welding phenomenon hardly occurs, the powder fluidity is not obviously reduced, the high sphericity is still maintained, and the problems of flattening, fragmentation and the like of particles in high-rotation speed and high-energy ball milling are overcome.
Drawings
Fig. 1 is an SEM picture of copper-chromium-niobium powder prepared in example one, wherein the spherical Cu powder is inlaid with irregularly shaped Cr powder and Nb powder on the surface.
Fig. 2 is a SEM picture and a spectrum composition distribution diagram of a cross section of the copper-chromium-niobium powder prepared in the first example.
Fig. 3 is a metallographic structure diagram of a copper-chromium-niobium alloy made by laser additive manufacturing of copper-chromium-niobium powder prepared in example one.
Fig. 4 SEM pictures and distribution diagrams of spectral components of the copper-chromium-niobium powder prepared in comparative example one.
Fig. 5 SEM pictures of the copper chromium niobium powder prepared in comparative example three.
Detailed Description
The present invention will be described in detail below with reference to the drawings and the detailed description, but the scope of the invention is not limited to the examples, but is still within the scope of the invention if those skilled in the art make some insubstantial improvements and modifications in the invention in light of the above disclosure.
Example 1
According to the components of Cu-8Cr-4Nb (atomic percent), namely Cu-6.5Cr-5.8Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere. And drying the pure chromium and pure niobium powder in a vacuum drying oven at 100 ℃ for 2 hours.
Under the protection of argon, the treated pure copper, pure chromium and pure niobium powder is put into a ball milling tank, ball milling is carried out at a low speed in a planet ball mill, the number of the used grinding balls is 1:1:1, the diameters of the grinding balls are 3mm, 6mm and 10mm, the weight ratio of the ball materials is 4:1, the ball milling rotating speed is 100rpm, the ball milling time is 4 hours, and the copper-chromium-niobium powder is obtained after the ball milling at a low speed.
The scanning electron microscope combined energy spectrum is adopted to test the copper-chromium-niobium powder, the copper powder is found to basically keep the spherical form of the original simple substance copper powder, a layer of chromium and niobium micropowder is inlaid on the surface of the copper powder, and the copper powder presents a sesame-like sphere structure, as shown in figures 1 and 2. The fluidity of the copper-chromium-niobium powder is measured to be 18s/50g by a Hall flowmeter; the powder has a reflectance of 32% at 1080nm by laser reflectometry. After the prepared copper-chromium-niobium powder is screened and separated for L-DED manufacture, the metallographic structure of the obtained copper-chromium-niobium alloy is shown as a figure 3, and the alloy contains a large number of chromium-niobium compound particles, almost no air holes and cracks; the alloy has a tensile strength of 391MPa at room temperature, an elongation after break of 11.6% and an electrical conductivity of 61.9% IACS.
Example two
According to the components of Cu-4Cr-2Nb (atomic percent), namely Cu-3.2Cr-2.9Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere, drying the pure chromium and pure niobium powder for 2 hours at 100 ℃ in a vacuum drying oven, putting the pure copper, pure chromium and pure niobium powder into a ball milling tank under the protection of argon, performing low-speed ball milling on the pure copper, pure chromium and pure niobium powder in a planetary ball mill, wherein the number of the used grinding balls is 3mm, 6mm and 10mm diameter copper balls in a 1:1:1 ratio, the weight ratio of the balls is 4:1, the ball milling rotating speed is 100rpm, the ball milling time is 4 hours, and obtaining the copper-chromium-niobium powder after low-speed ball milling. After L-DED manufacture by sieving and sorting the copper-chromium-niobium powder, the tensile strength is 371MPa, the elongation after break is 15.4%, and the conductivity is 63.6% IACS.
Example III
According to the components of Cu-2Cr-1Nb (atomic percent), namely Cu-1.6Cr-1.5Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere, drying the pure chromium and pure niobium powder for 2 hours at 100 ℃ in a vacuum drying oven, putting the pure copper, pure chromium and pure niobium powder into a ball milling tank under the protection of argon, and performing low-speed ball milling on the pure copper, pure chromium and pure niobium powder in a planetary ball mill, wherein the ball milling balls are copper balls with the diameters of 3mm, 6mm and 10mm in the number ratio of 1:1:1, the ball weight ratio is 4:1, the ball milling rotating speed is 100rpm, the ball milling time is 4 hours, and the copper-chromium-niobium powder is obtained after low-speed ball milling. After L-DED manufacture by sieving and sorting copper-chromium-niobium powder, the tensile strength is 305MPa, the elongation after break is 20.7%, and the conductivity is 68.3% IACS.
Example IV
According to the components of Cu-12Cr-6Nb (atomic percent), namely Cu-9.7Cr-8.7Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The grain diameter of the pure copper powder is 53-150 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere, drying the pure chromium and pure niobium powder for 2 hours at 100 ℃ in a vacuum drying oven, putting the pure copper, pure chromium and pure niobium powder into a ball milling tank under the protection of argon, and performing low-speed ball milling on the pure copper, pure chromium and pure niobium powder in a planetary ball mill, wherein the ball milling balls are copper balls with the diameters of 3mm, 6mm and 10mm in the number ratio of 1:1:1, the ball material weight ratio is 4:1, the ball milling rotating speed is 100rpm, the ball milling time is 4 hours, and the copper-chromium-niobium powder is obtained after the low-speed ball milling. After L-DED manufacture by sieving and sorting copper-chromium-niobium powder, the tensile strength is 409MPa, the elongation after breaking is 9.5%, and the conductivity is 55.9% IACS.
Example five
According to the components of Cu-8Cr-4Nb (atomic percent), namely Cu-6.5Cr-5.8Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere, drying the pure chromium and pure niobium powder for 2 hours at 100 ℃ in a vacuum drying oven, putting the pure copper, pure chromium and pure niobium powder into a ball milling tank under the protection of argon, and performing low-speed ball milling on the pure copper, pure chromium and pure niobium powder in a planetary ball mill, wherein the number of the used grinding balls is 3mm, 6mm and 10mm diameter copper balls in a 1:1:1 ratio, the ball weight ratio is 4:1, the ball milling rotating speed is 300rpm, the ball milling time is 1 hour, and the copper-chromium-niobium powder is obtained after the low-speed ball milling. After L-DED manufacture by sieving and sorting copper-chromium-niobium powder, the tensile strength is 380MPa, the elongation after break is 13%, and the conductivity is 63.2% IACS.
Comparative example one (elemental copper powder was not annealed)
According to the components of Cu-8Cr-4Nb (atomic percent), namely Cu-6.5Cr-5.8Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. Drying pure copper powder, pure chromium powder and pure niobium powder in a vacuum drying oven at 100 ℃ for 2 hours, putting the pure copper powder, the pure chromium powder and the pure niobium powder into a ball milling tank under the protection of argon, performing low-speed ball milling on the pure copper powder, the pure chromium powder, the pure niobium powder and the pure copper powder in a planetary ball mill, wherein the balls are copper balls with the diameters of 3mm, 6mm and 10mm in a number ratio of 1:1:1, the ball weight ratio is 4:1, the ball milling rotating speed is 100rpm, the ball milling time is 4 hours, and the mixed powder is obtained after the low-speed ball milling. The mixed powder is tested by adopting a scanning electron microscope and energy spectrum, and the chromium and niobium micro powder inlaid on the surface of the copper powder is little, as shown in figure 4. The powder had 67% reflectance of 1080nm laser light as measured by a laser reflectometer. After the mixed powder is screened and separated for L-DED manufacture, the internal holes are more, the tensile strength is 282MPa, the elongation after breaking is 12.6 percent, and the conductivity is 63.9 percent IACS. Metallographic photographs of the bulk samples showed significantly less chromium and niobium content inside the samples and some unfused areas were present.
Comparative example two
According to the components of Cu-8Cr-4Nb (atomic percent), namely Cu-6.5Cr-5.8Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain diameter of the pure chromium powder is 5-20 mu m, and the shape is spherical; the particle size of the pure niobium powder is 1-20 μm, and the shape is spherical. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere, drying the pure chromium and pure niobium powder for 2 hours at 100 ℃ in a vacuum drying oven, putting the pure copper, pure chromium and pure niobium powder into a ball milling tank under the protection of argon, performing low-speed ball milling on the pure copper, pure chromium and pure niobium powder in a planetary ball mill, wherein the number of the used grinding balls is 3mm, 6mm and 10mm diameter copper balls in a 1:1:1 ratio, the weight ratio of the balls is 4:1, the ball milling rotating speed is 100rpm, the ball milling time is 4 hours, and obtaining mixed powder after low-speed ball milling. The mixed powder is tested by adopting a scanning electron microscope and combining energy spectrum, and the chromium and niobium micro powder inlaid on the surface of the copper powder is little, and the chromium and niobium spherical powder is scattered around the copper powder. After L-DED production by sieving and sorting the mixed powder, the tensile strength was 291MPa, the elongation after break was 15.6%, and the electrical conductivity was 66.9% IACS. Metallographic photographs of the bulk samples showed significantly less chromium and niobium content inside the samples and some unfused areas were present.
Comparative example three
According to the components of Cu-8Cr-4Nb (atomic percent), namely Cu-6.5Cr-5.8Nb (weight percent), pure copper, pure chromium and pure niobium simple substance powder are respectively weighed. The particle size of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the particle size of the pure niobium powder is 5-20 μm, and the shape is irregular shape of mechanical crushing. And (3) annealing the pure copper powder for 4 hours at 500 ℃ under the protection of a reducing atmosphere, drying the pure chromium and pure niobium powder for 2 hours at 100 ℃ in a vacuum drying oven, putting the pure copper, pure chromium and pure niobium powder into a ball milling tank under the protection of argon, performing low-speed ball milling on the pure copper, pure chromium and pure niobium powder in a planetary ball mill, wherein the used grinding balls are copper balls with the diameters of 3mm, 6mm and 10mm in the number ratio of 1:1:1, the ball weight ratio is 4:1, the ball milling rotating speed is 350rpm, the ball milling time is 4 hours, and obtaining the mixed powder after low-speed ball milling. The mixed powder is tested by adopting a scanning electron microscope and energy spectrum, and chromium and niobium micro powder is inlaid on the surface of the copper powder, but the copper powder is severely flattened and disintegrated into an irregular shape as shown in figure 5. The hall flowmeter cannot smoothly fall down, and almost loses fluidity. The mixed powder is screened and separated to manufacture L-DED, powder feeding is not smooth, a powder feeding pipeline is blocked for many times, and preparation of a block sample cannot be realized.
The first to fifth embodiments realize laser material addition of high-performance copper-chromium-niobium blocks, which shows that good technical effects can be achieved within the technical feature combination and scope conforming to the limitation of the invention.
Comparing the first example with the first comparative example, it can be seen that if the pure copper powder is not sufficiently annealed and softened, the chromium and niobium micro powder is difficult to be smoothly embedded into the surface of the copper powder in the ball milling process, and the technical effect of the invention can not be realized.
By comparing the first example with the second example, it can be seen that if not adopting irregular chromium and niobium powder but adopting spherical chromium and niobium powder, the chromium and niobium powder are difficult to be effectively embedded into the surface of copper powder in the ball milling process, and the technical effect of the invention can not be realized.
From comparison of the first and third examples, it was found that if the ball milling speed exceeded the limit of the present invention, the copper powder was significantly deformed and broken, the powder flowability was severely lowered, and the powder feeding was not smooth, so that the L-DED production could not be completed.
Claims (8)
1. The copper-chromium-niobium composite powder for laser additive manufacturing is characterized in that: the copper-chromium-niobium composite powder is formed by compositing three components of copper, chromium and niobium, wherein the copper component is formed by micro-spherical copper simple substance powder, and the chromium component and the niobium component are respectively formed by irregularly-shaped chromium simple substance powder and niobium simple substance powder; the copper-chromium-niobium composite powder has a sesame-like sphere microstructure, namely: the chromium simple substance powder and the niobium simple substance powder with irregular shapes are inlaid on the surfaces of the copper microspheres to form the sesame-like sphere microstructure.
2. A copper chromium niobium composite powder for laser additive manufacturing as claimed in claim 1, wherein: the diameter of the copper microsphere is 180-200 mu m; the particle size range of the irregularly-shaped chromium simple substance powder and niobium simple substance powder is 5-20 mu m.
3. A method of preparing a copper chromium niobium composite powder for laser additive manufacturing according to claim 1 or 2, comprising the steps of:
1) Preparing simple substance powder: according to the total weight and the components of the copper-chromium-niobium alloy manufactured by the laser additive, calculating the amounts of pure copper, pure chromium and pure niobium single-substance powder respectively; wherein, the grain diameter of the pure copper powder is 180-200 mu m, and the shape is spherical; the grain size of the pure chromium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; the grain size of the pure niobium powder is 5-20 mu m, and the shape is an irregular shape of mechanical crushing; annealing the pure copper powder in a reducing atmosphere, and vacuum drying the pure chromium powder and the pure niobium powder;
2) Mixing and ball milling: under the protection of argon, putting pure copper powder, pure chromium powder and pure niobium powder into a ball milling tank for mixing, and performing low-speed ball milling in a planetary ball mill, wherein the ball milling speed is 100-300rpm, and the ball milling time is 2-4 hours; obtaining the copper-chromium-niobium composite powder with the sesame-like sphere microstructure.
4. A method for preparing the copper-chromium-niobium composite powder according to claim 3, wherein: and (3) annealing the pure copper powder in the step 1) in a reducing atmosphere at the temperature of 500 ℃ for 4 hours.
5. A method for preparing the copper-chromium-niobium composite powder according to claim 3, wherein: in the step 1), the pure chromium and pure niobium powder is dried in vacuum for 2 hours at 100 ℃ in a vacuum drying box.
6. A method for preparing the copper-chromium-niobium composite powder according to claim 3, wherein: the grinding balls used in the ball milling in the step 2) are copper balls with diameters of 3mm, 6mm and 10mm, and the number ratio of the copper balls to the copper balls is 1:1:1.
7. A method for preparing the copper-chromium-niobium composite powder according to claim 3, wherein: ball weight ratio of ball milling in step 2) is 4:1 or 6:1, wherein the ball weight ratio refers to the ratio of the weight of the grinding ball to the total weight of the abrasive, namely the ratio of the weight of the grinding ball to the total weight of pure copper powder, pure chromium powder and pure niobium powder.
8. The use of a copper-chromium-niobium composite powder according to claim 1 or 2, characterized in that the copper-chromium-niobium alloy is prepared by taking the copper-chromium-niobium composite powder as a raw material and adopting a powder feeding form and a laser additive manufacturing method.
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