CN115213424B - 3D printing method for high-elastic zinc alloy - Google Patents
3D printing method for high-elastic zinc alloy Download PDFInfo
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- CN115213424B CN115213424B CN202210685442.9A CN202210685442A CN115213424B CN 115213424 B CN115213424 B CN 115213424B CN 202210685442 A CN202210685442 A CN 202210685442A CN 115213424 B CN115213424 B CN 115213424B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/0003—Making bridge-work, inlays, implants or the like
- A61C13/0006—Production methods
- A61C13/0019—Production methods using three dimensional printing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/08—Artificial teeth; Making same
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/30—Platforms or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/02—Alloys based on zinc with copper as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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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
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- 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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Abstract
The invention provides a 3D printing method of a high-elasticity zinc alloy, which comprises the following steps: (1) preparing a zinc alloy additive, the zinc alloy additive comprising: 1% -7% of aluminum; 10% -30% of copper; 0.1% -2% of magnesium; lead is less than or equal to 0.004%; oxygen < 0.8%; iron < 0.8%; carbon < 0.8%; impurity < 2%; the balance of zinc; (2) And placing the zinc alloy additive into a 3D printer for printing, wherein the printed substrate is a zinc alloy substrate, the zinc content of the zinc alloy substrate is more than 90%, and introducing inert gas in the printing process. The high-elasticity zinc alloy 3D printing method provided by the embodiment of the invention can realize batch printing production of zinc alloy.
Description
Technical Field
The invention belongs to the technical field of zinc alloy 3D printing, and particularly relates to a high-elasticity zinc alloy 3D printing method.
Background
Zinc alloys are alloys based on zinc with other elements added. Commonly added alloying elements include aluminum, copper, magnesium, cadmium, titanium, and the like. The zinc alloy has the characteristics of low melting point, good fluidity, good casting formability, easy melting and plastic processing, and the waste materials are convenient to recycle and remelt. The existing zinc alloy processing mode adopts a casting forming mode for processing.
3D printing is a preparation technology for obtaining a product with a complex shape by using three-dimensional model data in a layer-by-layer accumulation mode. Compared with the traditional preparation methods of plastics, ceramics, metals and alloys and composite materials, the 3D printing technology has a series of advantages of preparing products with high precision and complex shapes, saving raw materials, saving cost and the like, and has good application prospect. Currently, the commonly used 3D printing method includes a direct three-dimensional printing forming technology (3 DP), a selective laser melting technology (SLM), a stereoscopic light curing technology (SLA), a fused deposition technology (FDM), etc., wherein the selective laser melting technology (SLM) is widely used for 3D printing of metal powder. The metals and alloys currently available for SLM are mainly stainless steel, titanium alloys, aluminum alloys, etc., and are mainly applied to the aerospace and automotive industries. The main research on metal printing by adopting 3D printing in the prior art is 3D printing of aluminum alloy and cobalt chromium molybdenum material. Some zinc alloy additives applicable to 3D printing are also developed on the market, for example, patent publication No. CN113308624A discloses a zinc alloy additive and a preparation method thereof, wherein the zinc alloy additive comprises more than 90 percent of zinc by weight; 1% -7% of aluminum; 0.1% -2% of magnesium; oxygen < 0.8%; iron < 0.8%; carbon < 0.8%; the impurity is less than 2 percent, wherein the sum of the weight percentages of the components is 100 percent. The zinc alloy additive and the zinc alloy obtained by the preparation method provided by the invention have the advantages of high elasticity and low melting point, and can be better used for preparing jewelry. However, the 3D printing technology of the zinc alloy is still immature, and particularly for zinc alloy with higher zinc content, the current 3D printing product yield is lower, and the mass production of the high-elasticity zinc alloy 3D printing is greatly limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-elastic zinc alloy 3D printing method capable of realizing a good zinc alloy 3D printing effect
The invention provides a 3D printing method of a high-elasticity zinc alloy, which comprises the following steps:
(1) Preparing a zinc alloy additive, the zinc alloy additive comprising: 1% -7% of aluminum; 10% -30% of copper; 0.1% -2% of magnesium; lead is less than or equal to 0.004%; oxygen < 0.8%; iron < 0.8%; carbon < 0.8%; impurity < 2%; the balance of zinc;
(2) And placing the zinc alloy additive into a 3D printer for printing, wherein the printed substrate is a zinc alloy substrate, the zinc content of the zinc alloy substrate is more than 90%, and introducing inert gas in the printing process.
Preferably, the zinc content of the zinc alloy substrate is greater than 95%.
Preferably, the copper is 15% -25%.
Preferably, the material of the zinc alloy substrate further comprises 2.8% -3.1% of aluminum; copper <0.030; magnesium 0.031% -0.07%; iron <0.020; other magazines are not more than 0.5%, and the balance is zinc.
Preferably, the zinc alloy substrate is a double-sided polished zinc alloy substrate.
Preferably, the zinc alloy substrate is cast by using an iron mold, and the periphery is machined.
Preferably, in the step (2), the laser power of the 3D printing is 80W-120W, and the marking speed of the 3D printing is more than 1200mm/s.
Preferably, the laser power of the 3D printing is 90W-110W, and the marking speed of the 3D printing is 1800mm/s-2200mm/s.
Preferably, in the step (2), the thickness of the powder coating is 0.02mm-0.05mm.
Preferably, the preparation method of the zinc alloy additive specifically comprises the following steps:
s1, putting the materials into a vacuum furnace according to a formula to carry out vacuumizing, wherein the vacuumizing pressure is-10 Pa;
s2, heating and melting, wherein the temperature of heating and melting is 460-480 ℃;
s3, placing metal liquid;
s4, introducing inert gas at a flow rate of 2000-4000 cubic meters per hour;
s5, crushing and atomizing the close-coupled spray disc, and simultaneously introducing metal liquid and inert gas into an atomizing device for atomization;
s6, performing flying cooling on a cooling tower with the tower diameter of 1750mm-1850mm and the tower height of 8000mm-10000 mm;
s7, separating the materials at the bottom of the cold-cut tower by cyclone separation, and collecting and storing the materials at the bottom of the tower;
s8, cold die press forming, wherein the die press forming pressure is as follows: 80-100 tons;
s9, vacuum sintering, wherein the vacuum sintering temperature is 120-160 ℃.
The high-elasticity zinc alloy 3D printing method provided by the embodiment of the invention can realize batch printing production of zinc alloy.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings. Like reference numerals refer to like parts throughout the drawings, and the drawings are not intentionally drawn to scale on actual size or the like, with emphasis on illustrating the principles of the invention.
FIG. 1 is a photograph of a printed product of example 1 of the present invention;
FIG. 2 is a photograph of a product printed in comparative example;
fig. 3 is a photograph of a zinc alloy substrate according to example 1 of the present invention.
Detailed Description
The following is a further detailed description of the present invention in conjunction with specific embodiments, so that those skilled in the art may better understand and practice the present invention, but the examples are not intended to limit the present invention.
The embodiment of the invention provides a 3D printing method of a high-elasticity zinc alloy, which comprises the following steps:
(1) Preparing a zinc alloy additive, the zinc alloy additive comprising: 1% -7% of aluminum; 10% -30% of copper; 0.1% -2% of magnesium; lead is less than or equal to 0.004%; oxygen < 0.8%; iron < 0.8%; carbon < 0.8%; impurity < 2%; the balance of zinc;
(2) And placing the zinc alloy additive into a 3D printer for printing, wherein the printed substrate is a zinc alloy substrate, the zinc content of the zinc alloy substrate is more than 90%, and introducing inert gas in the printing process.
According to the high-elastic zinc alloy 3D printing method provided by the embodiment of the invention, the zinc alloy substrate is adopted to print the zinc alloy additive, so that zinc alloy printing can be well attached to the zinc alloy substrate, the success of high-elastic zinc alloy 3D laser fusion is realized compared with the printing of stainless steel and 45-steel substrates, and the realization of mass production of high-elastic zinc alloy through 3D printing is realized.
The traditional 3D printing mode is poor in product adhesiveness when printing zinc alloy additive, and the traditional 304 stainless steel and 45# steel substrate only adapt to high-temperature metal 3D and print additive, and the effect that 3D printing fusion cannot be realized due to overburning oxidation can appear when printing zinc alloy additive, so that 3D printing of zinc alloy is difficult to realize batch production. The applicant has found through a number of experiments that if a zinc alloy substrate is used and is a substrate with a zinc content of more than 90% to print a high-elastic zinc alloy additive, the zinc alloy additive with a low melting point can be adapted.
In the embodiment, by increasing reasonable copper content, better forming effect is realized, and the yield of 3D printing is improved. And through the increase of copper content, the bonding strength of gold and porcelain is improved, so that the 3D printing method can be adopted to print qualified false teeth, and the false teeth can have a good gold and porcelain bonding effect.
In a preferred embodiment, the copper is 15% -25%. Reasonable copper content provides better shaping effect, promotes the artificial tooth's of zinc alloy 3D printing yield.
In a preferred embodiment, the zinc alloy substrate has a zinc content of greater than 95%. In a further preferred embodiment, the zinc alloy substrate has a zinc content of greater than 98%.
In a preferred embodiment, the material of the zinc alloy substrate further comprises 2.8% -3.1% of aluminum; copper <0.030; magnesium 0.031% -0.07%; iron <0.020; other magazines are not more than 0.5%, and the balance is zinc.
Referring to fig. 3, in a preferred embodiment, the zinc alloy substrate is a double-sided polished zinc alloy substrate, and the zinc alloy substrate provided in this embodiment is cast by using an iron mold, and is obtained by machining the periphery.
The zinc alloy base plate obtained by casting cannot be directly arranged on a precise 3D printer for use without machining, because the surface of the zinc alloy base plate is rough, the precision error is large, even burrs are still formed, the zinc alloy base plate can be installed for use only by machining to reach a certain precision, and otherwise, the due 3D printing effect cannot be obtained.
In a preferred embodiment, in the step (2), the laser power of the 3D printing is 80W-120W, and the marking speed of the 3D printing is more than 1200mm/s.
In a preferred embodiment, the laser power of 3D printing is 90W-110W, the marking speed of 3D printing is 1800mm/s-2200mm/s, and according to the zinc alloy additive formula, the characteristics of oxidation and gasification of 3D printing are easy to generate, and the laser power and the marking speed are adaptively adjusted.
In a preferred embodiment, in the step (2), the thickness of the powder coating is 0.02mm-0.05mm.
In a preferred embodiment, the preparation method of the zinc alloy additive specifically comprises the following steps:
s1, putting the materials into a vacuum furnace according to a formula to carry out vacuumizing, wherein the vacuumizing pressure is-10 Pa;
s2, heating and melting, wherein the temperature of heating and melting is 460-480 ℃;
s3, placing metal liquid;
s4, introducing inert gas at a flow rate of 2000-4000 cubic meters per hour;
s5, crushing and atomizing the close-coupled spray disc, and simultaneously introducing metal liquid and inert gas into an atomizing device for atomization;
s6, performing flying cooling on a cooling tower with the tower diameter of 1750mm-1850mm and the tower height of 8000mm-10000 mm;
s7, separating the materials at the bottom of the cold-cut tower by cyclone separation, and collecting and storing the materials at the bottom of the tower;
s8, cold die press forming, wherein the die press forming pressure is as follows: 80-100 tons;
s9, vacuum sintering, wherein the vacuum sintering temperature is 120-160 ℃.
According to the embodiment, a better powder refining effect is achieved through crushing and atomizing of the close-coupled spray disc, and meanwhile, an effect of low oxygen content of particles is achieved through high-speed introduction of inert gas in the atomizing process. And the high-speed inert gas is introduced, so that the effect of atomizing metal and crushing can be achieved, and the zinc alloy additive prepared by matching with an alloy formula of zinc alloy has better performance and can be used for preparing metal ornaments.
According to the embodiment, the cooling tower is used for carrying out flight cooling, the cyclone separation device is used for separation, the cost is low, the preparation of small-particle powder can be better realized, the prepared alloy powder is small in particle size, and the particle size is uniform. The product is ensured to be solid spherical powder, and better product molding is ensured, so that the alloy performance is better.
For a further understanding and appreciation of the inventive aspects, a further description of the preferred embodiments will now be provided.
Example 1
Preparing zinc alloy additive:
the formula is as follows: 1% -7% of aluminum; 10% -20% of copper; 0.1% -2% of magnesium; lead is less than or equal to 0.004%; oxygen < 0.8%; iron < 0.8%; carbon < 0.8%; impurity < 2%; the balance being zinc.
The preparation method comprises the following steps:
s1, putting the materials into a vacuum furnace according to a formula to carry out vacuumizing, wherein the vacuumizing pressure is-10 Pa;
s2, heating and melting, wherein the temperature of heating and melting is 460-480 ℃;
s3, placing metal liquid;
s4, introducing inert gas at a flow rate of 2000-4000 cubic meters per hour;
s5, crushing and atomizing the close-coupled spray disc, and simultaneously introducing metal liquid and inert gas into an atomizing device for atomization;
s6, performing flying cooling on a cooling tower with the tower diameter of 1750mm-1850mm and the tower height of 8000mm-10000 mm;
s7, separating the materials at the bottom of the cold-cut tower by cyclone separation, and collecting and storing the materials at the bottom of the tower;
s8, cold die press forming, wherein the die press forming pressure is as follows: 80-100 tons;
s9, vacuum sintering, wherein the vacuum sintering temperature is 120-160 ℃.
3D printing is carried out on the alloy additive by adopting a DiMetal-100 metal 3D printing device, and the laser power is 100W; marking speed is 2000mm/s, and t2 slice thickness (namely powder coating thickness) is 0.03mm; in the printing process, the protection of argon is enhanced, and the zinc alloy is prevented from being gasified.
The materials of the printing substrate are as follows: 2.8% -3.1% of aluminum; copper <0.030; magnesium 0.031% -0.07%; iron <0.020; other magazines are not more than 0.5%, and the balance is zinc. The printing substrate is polished on two sides and is obtained after four-side machining.
The printed product is shown in figure 1, and the product has good integrity. Among 500 cylindrical products printed, 478 products without defects are printed, and the yield reaches 95%.
Example 2
In example 2, a model of the denture was designed in advance before 3D printing, and then 3D printing was performed, as compared with example 1. Other preparation methods and formulations were the same as in example 1. Can realize the printing and forming of false teeth, and the number of the 10 false tooth products printed is 9 without defects, so that the yield is higher.
The printed false tooth adopts a three-point bending method to test the bonding strength of gold and porcelain according to the YY 0.621.1-2016 standard, the bonding strength of gold and porcelain is 32Mpa, and the bonding strength of gold and porcelain is poor and only 16Mpa when the copper content is lower and only 5% is obtained on the basis of the formula and the preparation method. The false tooth prepared by the embodiment has higher gold porcelain bonding strength.
The linear expansion coefficient was measured according to the method in the GB17168-2013 standard and was 13.1 (10 -6/ k)。
The tarnish resistance test is carried out with reference to GB17168-2013-8.6, if there is only a slight color change and rust on the alloy can be easily removed by a slight brushing, the tarnish resistance is judged to be present, otherwise the tarnish resistance is judged not to be present. Testing resulted in "having" tarnish resistance.
Corrosion resistance tests were carried out with reference to GB17168-2013-8.5, and should not exceed 200ug/cm 2 If the number exceeds the predetermined number, the test result is judged as being failed, and if the number does not exceed the predetermined number, the test result is judged as being qualified. The product test of this example was acceptable.
Comparative example
In comparison with example 1, the substrate used in comparative example 1 was different, the stainless steel substrate was used in comparative example 1, and the other zinc alloy formulation and 3D printing method were the same as in example 1. The printed product is shown in figure 2, and it can be seen that the zinc alloy printing is performed by adopting the stainless steel substrate, so that the product adhesiveness is poor, and the printing and forming can not be successfully performed.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.
Claims (2)
1. The 3D printing method for the high-elastic zinc alloy is characterized by comprising the following steps of:
(1) Preparing a zinc alloy additive, the zinc alloy additive comprising: 1% -7% of aluminum; 15% -25% of copper; 0.1% -2% of magnesium; lead is less than or equal to 0.004%; oxygen < 0.8%; iron < 0.8%; carbon < 0.8%; impurity < 2%; the balance of zinc;
(2) Putting the zinc alloy additive into a 3D printer for printing, wherein the printed substrate is a zinc alloy substrate, the zinc content of the zinc alloy substrate is more than 95%, and introducing inert gas in the printing process;
the material of the zinc alloy substrate also comprises 2.8% -3.1% of aluminum; copper <0.030; magnesium 0.031% -0.07%; iron <0.020; other impurities are not more than 0.5%, and the balance is zinc;
the zinc alloy substrate is a double-sided polished zinc alloy substrate;
the zinc alloy substrate is cast by using an iron mold, and the periphery of the zinc alloy substrate is obtained after machining;
the zinc alloy 3D printing method adopts a DiMetal-100 metal 3D printing device to carry out 3D printing; the laser power of the 3D printing is 90W-110W, and the marking speed of the 3D printing is 1800mm/s-2200 mm/s;
in the step (2), the thickness of the powder coating is 0.02mm-0.05mm.
2. The method for 3D printing of high-elastic zinc alloy according to claim 1, wherein the method for preparing the zinc alloy additive comprises the following steps:
s1, putting the materials into a vacuum furnace according to a formula to carry out vacuumizing, wherein the vacuumizing pressure is-10 Pa;
s2, heating and melting, wherein the temperature of heating and melting is 460-480 ℃;
s3, placing metal liquid;
s4, introducing inert gas at a flow rate of 2000-4000 cubic meters per hour;
s5, crushing and atomizing the close-coupled spray disc, and simultaneously introducing metal liquid and inert gas into an atomizing device for atomization;
s6, performing flying cooling on a cooling tower with the tower diameter of 1750mm-1850mm and the tower height of 8000mm-10000 mm;
s7, separating the materials at the bottom of the cooling tower by cyclone separation, and collecting and storing the materials at the bottom of the cooling tower.
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| CN108113786A (en) * | 2017-12-14 | 2018-06-05 | 暨南大学 | The method that personalized degradable metal stent or internal fixation device part are prepared based on 3D printing |
| CN109365811B (en) * | 2018-11-27 | 2021-07-06 | 北京科技大学广州新材料研究院 | Method for forming zinc alloy product by selective laser melting technology |
| RU2730821C1 (en) * | 2019-12-27 | 2020-08-26 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Heat resistant aluminum powder material |
| CN111850332A (en) * | 2020-06-30 | 2020-10-30 | 同济大学 | 3D printing process method of high-strength aluminum-zinc alloy |
| CN113308624B (en) * | 2021-04-20 | 2024-02-23 | 广州湘龙高新材料科技股份有限公司 | Zinc alloy additive and preparation method thereof |
| CN113275577A (en) * | 2021-04-20 | 2021-08-20 | 广州湘龙高新材料科技股份有限公司 | Preparation method of zinc alloy additive |
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