CN114272863B - Preparation method of core-shell structure composite microspheres - Google Patents
Preparation method of core-shell structure composite microspheres Download PDFInfo
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- CN114272863B CN114272863B CN202111601943.6A CN202111601943A CN114272863B CN 114272863 B CN114272863 B CN 114272863B CN 202111601943 A CN202111601943 A CN 202111601943A CN 114272863 B CN114272863 B CN 114272863B
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Abstract
The invention discloses a preparation method of a core-shell structure composite microsphere, which comprises core layer metal and shell layer metal, wherein the melting point of the shell layer metal is lower than that of the core layer metal; the preparation method specifically comprises the following steps: s1, wrapping a nuclear layer metal wire with a shell layer metal strap to obtain a bimetallic wire; s2, shearing the bimetallic wire and then carrying out plasma spheroidization treatment to obtain the core-shell structure composite microsphere. The method disclosed by the invention is clean and environment-friendly, each obtained microsphere is of a core-shell composite structure, the content ratio and the size of metal of a core layer and metal of a shell layer of the microsphere are convenient to regulate and control, and the use requirements of different scenes can be met.
Description
Technical Field
The invention belongs to the technical field of powder materials, and particularly relates to a preparation method of a core-shell structure composite microsphere.
Background
The core-shell structure is an ordered assembly structure formed by coating one material with another material through chemical bonds or other acting forces. The core and the shell which form the core-shell structure are two materials with different properties, the purpose of improving the property of a single particle is achieved through the core-shell coating mode, and the function which cannot be achieved by any single material can be generated through the mutual matching effect of the two core-shell materials under special conditions.
The core-shell structure composite microsphere is a novel composite material, and has wide application prospect in the fields of powder metallurgy, electronics and electricity and the like. For example, the core-shell structure solder ball is a micro solder ball which is adopted in the field of advanced microelectronic packaging, the core-shell structure solder ball takes a high-conductivity, high-strength and high-melting-point material as an alloy, and the outer surface of the core-shell structure solder ball is covered by soft lead solder, so that the conductivity and heat conductivity of a welding spot can be obviously improved; for another example, the core-shell structure bimetal composite welding powder using copper or copper-based alloy as a core and tin or tin-based alloy as a shell can be melted at a lower temperature while preventing copper and copper alloy from being oxidized due to direct contact with the outside, thereby promoting the welding and sintering of copper and copper alloy, reducing the overall brazing temperature, saving energy, reducing consumption and reducing thermal shock to the welded parent metal.
However, the current industrial preparation method is mainly limited to an electroplating method, the electroplating process is complex, the control difficulty is high, the thickness of a shell layer obtained by electroplating cannot be accurately controlled, a core-shell structure composite solder ball with a thicker shell layer is difficult to obtain, the uniformity of a product is difficult to ensure, the weldability is poor, and the electroplating processing is restricted by various factors due to the characteristics of the electroplating industrial production when clean and green production is advocated. Other documents report that the shell-core structure microspheres prepared by using a rotary centrifugal atomization method are difficult to ensure that each microsphere is of a core-shell structure, and the uniformity of components cannot be guaranteed. Therefore, it is urgently needed to develop a preparation method of a novel core-shell structure composite microsphere with simple process and controllable product quality.
Disclosure of Invention
Based on the technical problem, the invention provides a preparation method of a core-shell structure composite microsphere. The method is clean and environment-friendly, and the obtained core-shell structure composite microspheres have good size and content uniformity and are convenient to regulate and control, so that the use requirements of different scenes can be met.
The specific scheme of the invention is as follows:
a preparation method of a core-shell structure composite microsphere comprises a core layer metal and a shell layer metal, wherein the melting point of the shell layer metal is lower than that of the core layer metal; the preparation method specifically comprises the following steps: s1, wrapping a nuclear layer metal wire with a shell layer metal belt to obtain a bimetallic wire; and S2, shearing the bimetallic wire and then carrying out plasma spheroidization treatment to obtain the core-shell structure composite microsphere.
Preferably, the metal of the core layer is selected from any one metal or metal alloy of copper, aluminum, gold, silver, nickel, iron and tungsten; the shell metal is selected from any one metal or metal alloy of tin, silver, copper, aluminum, gold, silver, nickel and iron.
Preferably, the core-shell structure composite microsphere is a Cu @ Sn composite microsphere, copper or copper alloy is taken as core layer metal, and tin or tin alloy is taken as shell layer metal. The core-shell structure composite microsphere is expressed as a ' core layer metal ' shell layer metal ' composite microsphere.
Preferably, in S1, the thickness of the shell metal belt is 0.01-0.1mm; the diameter of the metal wire of the nuclear layer is 0.1-0.5mm.
The shell metal band and the core metal wire adopted by the invention can be commercially available finished products, and the specification of the finished product is selected according to the target size of the core-shell structure composite microsphere. The shell metal band can be manufactured by the existing method according to the target size except for directly utilizing the commercial products, so that the free adjustment of the size of the core-shell structure composite microsphere is ensured. For example, when preparing the Cu @ Sn composite microspheres, the tin ribbon can be obtained by smelting, ingot casting, head cutting, extruding, rolling, cutting, cleaning and coiling a high-purity tin ingot according to the method disclosed in 'development of high-purity tin ribbon for fuse and transverse thickness difference control' of a plurality of hundred wins.
Preferably, in S1, the core layer metal wire and the shell layer metal belt are bonded by an adhesive; when the number of the layers wrapped by the shell metal belt is more than or equal to 2, the layers of the shell metal belt are bonded by the adhesive.
The adhesive used for bonding the core layer metal wire and the shell layer metal band layers in the present invention is not particularly limited, and includes, but is not limited to: polyisobutylene, rosin alcohol solution, polyethylene glycol, and the like.
Preferably, in S2, the bimetallic wire is sheared to a length of 0.1-0.6mm. Shearing to obtain a plurality of columnar bimetal materials with the length of 0.1-0.6mm.
Preferably, in S2, the specific parameters of the plasma spheroidizing process are as follows: the powder feeding speed is 5-30g/min, the carrier gas flow is 1-5L/min, and the plasma power is 15-50kW.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with an electroplating method, the method is cleaner and more environment-friendly, and has the advantages of simple method and high material utilization rate;
(2) The method can obtain the spherical or nearly spherical core-shell structure composite microspheres with uniform content and size;
(3) According to the invention, the flexible regulation and control of different mass ratios of the core layer metal and the shell layer metal and the particle size of the composite microsphere can be realized by regulating and controlling the diameter of the core layer metal wire, the thickness of the shell layer metal band and the number of the layers of the metal wire wrapped by the shell layer metal band, so that the use requirements under different scenes are met.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
The Cu @ Sn composite microsphere comprises core layer metal Cu and shell layer metal Sn, wherein the content of the shell layer metal Sn accounts for 15% of the total amount of the composite microsphere; wherein Cu is red copper with the purity of more than 99.9 percent, and Sn is pure tin with the purity of more than 99.9 percent.
The preparation method specifically comprises the following steps:
s1, wrapping a tin tape with the specification (width and thickness) of 30 multiplied by 0.01mm with a copper wire with the specification (diameter) of 0.20mm, wherein the number of wrapping layers is 1, so as to obtain a bimetallic wire; the tin tape and the copper wire are bonded by using a rosin alcohol solution as a bonding agent, wherein the mass ratio of rosin to alcohol is 1;
s2, cutting the bimetallic wire into a plurality of bimetallic wires with the lengths of 0.3mm, and then carrying out plasma spheroidizing treatment, wherein the specific parameters are as follows: the powder feeding rate is 30g/min, the carrier gas flow is 5L/min, the plasma power is 25kW, and the composite microsphere with the average particle size of 0.25mm Cu @ Sn is obtained.
Example 2
The Cu @ Sn composite microsphere comprises core layer metal Cu and shell layer metal Sn, wherein the content of the shell layer metal Sn accounts for 35% of the total amount of the composite microsphere; wherein Cu is red copper with purity of more than 99.9%, and Sn is pure tin with purity of more than 99.9%.
The preparation method specifically comprises the following steps:
s1, wrapping a tin tape with the specification (width and thickness) of 30 multiplied by 0.03mm with a copper wire with the specification (diameter) of 0.20mm, wherein the number of wrapping layers is 1, so as to obtain a bimetallic wire; the solder strip and the copper wire are bonded by using a rosin alcohol solution as an adhesive, and the mass ratio of rosin to alcohol is 1;
s2, cutting the bimetallic wire into a plurality of bimetallic wires with the lengths of 0.3mm, and then carrying out plasma spheroidizing treatment, wherein the specific parameters are as follows: the powder feeding rate is 30g/min, the carrier gas flow is 5L/min, the plasma power is 25kW, and the composite microsphere with the average particle size of 0.28mm Cu @ Sn is obtained.
Example 3
The Cu @ Al composite microsphere comprises core layer metal Cu and shell layer metal Al, wherein the content of the shell layer metal Al accounts for 10% of the total amount of the composite microsphere; wherein Cu is red copper with the purity of more than 99.9 percent, and Al is pure aluminum with the purity of more than 99.0 percent.
The preparation method specifically comprises the following steps:
s1, wrapping a copper wire with the specification (diameter) of 0.50mm by an aluminum strip with the specification (width is multiplied by thickness) of 30 multiplied by 0.02mm, wherein the number of wrapping layers is 2, so as to obtain a bimetallic wire; wherein, polyisobutylene with molecular weight 2300 is adopted as a binder to bond between the aluminum strips and the copper wires and between the 2 layers of aluminum strips;
s2, cutting the bimetallic wire into a plurality of bimetallic wires with the lengths of 0.5mm, and then carrying out plasma spheroidization treatment, wherein the specific parameters are as follows: the powder feeding speed is 15g/min, the carrier gas flow is 3L/min, the plasma power is 30kW, and the composite microsphere with the average particle size of 0.51mmCu @ Al is obtained.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (6)
1. The preparation method of the core-shell structure composite microsphere is characterized in that the core-shell structure composite microsphere comprises core layer metal and shell layer metal, and the melting point of the shell layer metal is lower than that of the core layer metal; the preparation method specifically comprises the following steps: s1, wrapping a nuclear layer metal wire with a shell layer metal belt to obtain a bimetallic wire; s2, shearing the bimetallic wire and then carrying out plasma spheroidization treatment to obtain the core-shell structure composite microsphere; in S1, the thickness of a shell metal belt is 0.01-0.1mm; the diameter of the metal wire of the nuclear layer is 0.1-0.5mm.
2. The preparation method of the core-shell structure composite microsphere according to claim 1, wherein the core layer metal is selected from any one of pure metals or metal alloys of copper, aluminum, gold, silver, nickel, iron and tungsten; the shell metal is selected from any one of tin, silver, copper, aluminum, gold, nickel and iron or metal alloy.
3. The preparation method of the core-shell structure composite microsphere according to claim 1 or 2, wherein the core-shell structure composite microsphere is a Cu @ Sn composite microsphere, copper or copper alloy is used as core layer metal, and tin or tin alloy is used as shell layer metal.
4. The preparation method of the core-shell structure composite microsphere according to claim 1 or 2, wherein in S1, the metal wires of the core layer and the metal bands of the shell layer are bonded by an adhesive; when the number of the layers wrapped by the shell metal belt is more than or equal to 2, the layers of the shell metal belt are bonded by the adhesive.
5. The method for preparing the core-shell structure composite microspheres according to claim 1 or 2, wherein in S2, the bimetallic wire is sheared to a length of 0.1-0.6mm.
6. The preparation method of the core-shell structure composite microsphere according to claim 1 or 2, wherein in S2, specific parameters of plasma spheroidization treatment are as follows: the powder feeding speed is 5-30g/min, the carrier gas flow is 1-5L/min, and the plasma power is 15-50kW.
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| JP3426403B2 (en) * | 1995-05-12 | 2003-07-14 | 新日本製鐵株式会社 | Manufacturing method of fine metal sphere |
| CN100417489C (en) * | 2005-10-13 | 2008-09-10 | 河南科技大学 | Wire cutting type processing equipment and method for high sealing use brazed ball |
| CN104550943B (en) * | 2015-01-28 | 2017-09-15 | 中国科学院过程工程研究所 | A kind of spherical copper cladding tungsten composite powder, preparation method and its usage |
| CN104999076B (en) * | 2015-06-01 | 2017-11-17 | 浙江亚通焊材有限公司 | The method that one kettle way prepares the controllable silver-colored copper-clad nano-powder of shell thickness |
| CN109570521A (en) * | 2018-12-24 | 2019-04-05 | 南通金源智能技术有限公司 | The method that plasma spheroidization prepares metal powder |
| CN112276382B (en) * | 2020-10-29 | 2022-08-23 | 北京科技大学顺德研究生院 | Method for preparing metal shots by laser cutting |
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