CN108115308B - Al (aluminum)18B4O33Whisker reinforced silver-copper composite solder and preparation method thereof - Google Patents
Al (aluminum)18B4O33Whisker reinforced silver-copper composite solder and preparation method thereof Download PDFInfo
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- CN108115308B CN108115308B CN201810004388.0A CN201810004388A CN108115308B CN 108115308 B CN108115308 B CN 108115308B CN 201810004388 A CN201810004388 A CN 201810004388A CN 108115308 B CN108115308 B CN 108115308B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
The invention discloses Al18B4O33The whisker reinforced silver-copper composite solder comprises, by mass, 60-70% of Ag powder, 20-30% of Cu powder and 5-15% of Al18B4O33And (5) preparing the whisker. The preparation method comprises the following steps: 1. weighing 60-70% of Ag powder, 20-30% of Cu powder and 5-15% of Al according to mass percentage18B4O33Whisker, mixing to obtain original solder powder; 2. placing the original brazing filler metal powder and the grinding balls obtained in the step 1 into a planetary ball milling tank, vacuumizing, then filling argon into the ball milling tank, and carrying out ball milling for 2-8 hours at the rotating speed of 100-150 r/min to obtain Al18B4O33The crystal whisker reinforced silver-copper composite solder. The invention improves the welding strength.
Description
Technical Field
The invention belongs to the technical field of welding, and relates to a whisker reinforced silver-copper composite solder and a preparation method thereof, which are used for ceramic/ceramic or ceramic/metal brazing.
Background
The ceramic material is widely applied to the fields of aerospace, electronics, chemical engineering, nuclear and the like by virtue of the advantages of high temperature resistance, corrosion resistance, wear resistance, low density, high strength and the like. However, ceramic materials are brittle and difficult to manufacture into large and complex components, and thus, the ceramic materials need to be welded to themselves or connected with metals to manufacture components meeting the use requirements. Among the many joining methods, brazing is the simplest and practical method for ceramic joining. However, the physical properties of the ceramic and metal base materials and the ceramic base material and metal brazing seam are greatly different, and a large residual stress is likely to be formed in the joint.
The existing method for relieving the residual stress of the ceramic soldered joint by using the composite solder has two methods: firstly, adding a particle reinforcing phase into the brazing filler metal, and secondly, generating crystal whiskers in situ; the two methods can improve the difference of the linear expansion coefficients between the brazing seam and the ceramic base metal, and further reduce the residual stress of the joint.
However, the disadvantages of the first method are: when particles with low linear expansion coefficient, especially nano-sized particles, are added into the metal solder as a reinforcing phase, the added particles are easy to agglomerate, thereby weakening the improvement effect; and the mechanical property of the particle reinforced phase can not be fully embodied, and the limiting effect on the plastic deformation of the surrounding metal is limited. The second method has the following disadvantages: when the whiskers generated through the in-situ reaction strengthen the joint, the brazing time is short, the generated whiskers are small in quantity and relatively small in size, the distribution of the whiskers is limited by the original distribution position of reactant particles to a certain extent, and the strengthening form is often dependent on the vacuum condition.
Disclosure of Invention
Aiming at the problems of the existing composite solder, the invention aims to provide Al18B4O33The whisker reinforced silver-copper composite brazing filler metal is used for uniformly distributing one-dimensional single crystals of a reinforcing phase in brazing seams, the number, distribution, size and application conditions of the reinforcing phase are not limited, and the strength of a brazing joint can be improved. The invention also provides Al18B4O33A method for preparing whisker reinforced silver-copper composite solder.
The invention provides Al18B4O33The whisker reinforced silver-copper composite solder comprises, by mass, 60% -70% of Ag powder, 20% -30% of Cu powder and 5% -15% of Al18B4O33And (5) preparing the whisker.
The invention provides Al18B4O33The preparation method of the whisker reinforced silver-copper composite solder comprises the following steps:
step 1, weighing 60-70% of Ag powder, 20-30% of Cu powder and 5-15% of Al powder according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
step 2, placing the original brazing filler metal powder and the grinding balls obtained in the step 1 into a planetary ball milling tank, and vacuumizing the tankArgon is filled into the ball milling tank, and ball milling is carried out for 2-8 h at the rotating speed of 100-150 r/min to obtain Al18B4O33The crystal whisker reinforced silver-copper composite solder.
The invention has the technical effects that:
al of the invention18B4O33In the whisker reinforced silver-copper composite solder, Ag and Cu are matrix elements, and Al18B4O33The whiskers are a reinforcing phase added directly to the solder powder. Ag and Cu can form liquid phase through eutectic reaction under the vacuum condition, gaps among welded parent metals are filled, and the residual liquid phase after reaction is solidified in the cooling process to form a metal matrix part of a brazing seam; under the condition of air, Cu element is oxidized to generate CuO along with the increase of temperature, Ag passes through the eutectic liquid phase formed by the CuO and fills the gap between the welded parent metal, and the Ag in the liquid phase forms the metal matrix part of the brazing seam after being cooled. In the present invention, Al is selected18B4O33The whisker as a reinforcing phase has four advantages:
1、Al18B4O33the synthesis process of the whisker is a stacking process of atoms on a high-energy plane, the growth direction (length direction) of the whisker is vertical to the high-energy plane, and therefore Al is enabled to be contained18B4O33In the atoms on the surface of the crystal whisker, the atomic number ratio with higher energy is much smaller than that of the nano particles, so that the agglomeration tendency of a reinforcing phase in the preparation process of the composite solder is greatly reduced, and the obtained composite solder has good uniformity;
2、Al18B4O33the crystal whisker has a single crystal structure, has few self defects and high mechanical strength, and the formed composite brazing seam containing the crystal whisker can absorb more energy through the fracture and deflection of the crystal whisker, thereby improving the bearing capacity of a brazing joint;
3. by direct addition of Al18B4O33The whisker is taken as a reinforcing phase, so that the dependence of the reported whisker reinforcement on in-situ synthesis conditions (such as vacuum conditions) can be overcome, and the application range of the prepared composite solder is expanded;
4、Al18B4O33whisker producing toolThe process is mature, and the raw materials are low in price, so that the composite solder prepared by using the composite solder as the reinforcing phase is relatively low in cost.
The composite solder of the invention is adopted to braze Al in air at 1050 DEG C2O3When made of ceramics, a large amount of Al is uniformly distributed in the obtained soldered joint18B4O33The crystal whisker reinforcing phase has a size obviously larger than that of the crystal whisker synthesized in situ, and part of Al18B4O33The whisker has been broken off, indicating that Al18B4O33The crystal whisker has the function of fully absorbing energy, the average shearing strength of a soldered joint can reach 61MPa, and the soldering joint has the shearing strength improved by 154 percent compared with the soldering joint for air soldering of aluminum oxide ceramics by using silver-copper solder, and is more than 2 times of the silver-copper solder.
Drawings
The drawings of the invention are illustrated as follows:
FIG. 1 shows Al prepared in example 118B4O33Scanning photos of microscopic morphology secondary electrons of the whisker reinforced silver-copper composite solder;
FIG. 2 is a microstructure topography of the welded sheet of example 1;
FIG. 3 shows Al in example 12O3And (4) a fracture picture of the ceramic brazed joint.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
example 1
In this example, 65% of Ag powder, 25% of Cu powder and 10% of Al powder are weighed according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
placing the original brazing filler metal powder and grinding balls in a planetary ball milling tank, vacuumizing, then filling argon into the ball milling tank, and carrying out ball milling for 4 hours at the rotating speed of 120r/min to obtain Al18B4O33Whisker reinforced silver-copper composite solder; wherein the ball-material ratio is 9:1, and the filler ratio is 45%.
The ball material ratio refers to the ratio of the mass of the ceramic grinding ball used in ball milling to the mass of the prepared brazing filler metal; the filler ratio is the ratio of the total volume of the grinding balls and the brazing filler metal powder to the volume of the ball milling tank.
Test 1:
for Al prepared as above18B4O33The microscopic morphology of the whisker reinforced silver-copper composite solder is observed by a scanning electron microscope, and as can be seen from figure 1, the whisker reinforced phase in the composite solder is uniformly distributed, and no obvious reinforced phase agglomeration phenomenon is observed.
And (3) testing 2:
two pieces of Al with the size of 8mm multiplied by 5mm are taken2O3The welded surfaces of the ceramic base materials are polished by using No. 600 and No. 1000 diamond grinding wheels, then the polished surfaces are polished to the roughness of 1 mu m, after ultrasonic cleaning in acetone solution, the composite brazing filler metal prepared by the embodiment is used for connecting two base materials by adopting a tiling preset mode, and heat preservation is carried out for 10min at the connection temperature of 1050 ℃ under the air condition, so that the sample 1 is obtained.
By using a diamond wire cutting method, a sheet having a thickness of 2mm was cut out from the sample 1 obtained in test 1, and after grinding and polishing with a 600#, 1000#, 1200# diamond grinding wheel, a welded sheet 1 was obtained.
FIG. 2 is a microstructure of the welded sheet 1, and it can be seen from FIG. 2 that a large amount of Al is uniformly distributed in the brazing seams of the obtained brazed joint18B4O33The crystal whisker reinforcing phase has a size obviously larger than that of the crystal whisker synthesized in situ, and part of Al18B4O33The whisker has been broken off, indicating that Al18B4O33The whiskers can fully absorb energy.
And (3) testing:
taking three pairs of Al with the dimensions of 15mm multiplied by 10mm multiplied by 5mm and 8mm multiplied by 5mm2O3The ceramic base material is manufactured into 3 samples by the method of the test 1, the 3 samples are subjected to a shearing test, and an average value is obtained.
Al of the present example18B4O33Whisker reinforced silver-copper composite solder air brazing Al2O3The average shear strength of the soldered joint obtained from the ceramic can reach 61MPa, and similarly, the shear strength of the soldered joint obtained from the silver-copper solderThe degree is 24 MPa, and the shearing strength of the soldered joint is improved by 154 percent compared with that of the soldered joint using silver-copper solder for air soldering of alumina ceramics.
FIG. 3 shows Al of this example2O3Fracture photograph of ceramic brazed joint from which a large amount of Al was observed18B4O33The whisker and the nest groove left after the whisker is pulled out.
Thus, the Al of the present invention can be obtained18B4O33The whisker reinforced silver-copper composite solder can realize high-quality brazing of ceramic materials, and Al in brazed joints18B4O33On one hand, the whisker reinforced phase can reduce the linear expansion coefficient of the whole brazing seam, and can absorb extra energy through self breaking and deflection, thereby obviously improving the connection quality of the ceramic brazing joint.
Example 2
In this embodiment, 60% of Ag powder, 30% of Cu powder and 10% of Al are weighed according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
placing the original brazing filler metal powder and grinding balls in a planetary ball milling tank, vacuumizing, filling argon into the ball milling tank, and ball milling for 2 hours at the rotating speed of 100r/min to obtain Al18B4O33Whisker reinforced silver-copper composite solder; wherein the ball-to-material ratio is 6:1, and the filling ratio is 40%.
The test was carried out in accordance with test 3 of example 1, Al of this example18B4O33Whisker reinforced silver-copper composite solder air brazing Al2O3The average shearing strength of the brazing joint obtained by the ceramic is 45 MPa.
Example 3
In this example, 70% of Ag powder, 20% of Cu powder and 10% of Al are weighed according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
placing the original brazing filler metal powder and grinding balls in a planetary ball milling tank, vacuumizing, then filling argon into the ball milling tank, and carrying out ball milling for 8 hours at the rotating speed of 150r/min to obtain Al18B4O33Whisker reinforcementThe silver-copper composite solder; wherein the ball-material ratio is 12:1, and the filler ratio is 50%.
The test was carried out in accordance with test 3 of example 1, Al of this example18B4O33Whisker reinforced silver-copper composite solder air brazing Al2O3The average shearing strength of the brazing joint obtained by the ceramic is 58 MPa.
Example 4
In this example, 68.4% of Ag powder, 26.6% of Cu powder and 5% of Al powder are weighed according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
placing the original brazing filler metal powder and grinding balls in a planetary ball milling tank, vacuumizing, then filling argon into the ball milling tank, and carrying out ball milling for 4 hours at the rotating speed of 120r/min to obtain Al18B4O33Whisker reinforced silver-copper composite solder; wherein the ball-material ratio is 9:1, and the filler ratio is 45%.
The test was carried out in accordance with test 3 of example 1, Al of this example18B4O33Whisker reinforced silver-copper composite solder air brazing Al2O3The average shearing strength of the brazing joint obtained by the ceramic is 47 MPa.
Example 5
In this example, 61.2% of Ag powder, 23.8% of Cu powder and 15% of Al powder are weighed according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
placing the original brazing filler metal powder and grinding balls in a planetary ball milling tank, vacuumizing, then filling argon into the ball milling tank, and carrying out ball milling for 4 hours at the rotating speed of 120r/min to obtain Al18B4O33Whisker reinforced silver-copper composite solder; wherein the ball-material ratio is 9:1, and the filler ratio is 45%.
The test was carried out in accordance with test 3 of example 1, Al of this example18B4O33Whisker reinforced silver-copper composite solder air brazing Al2O3The average shearing strength of the brazed joint obtained by the ceramic is 32 MPa.
The above-mentioned Ag powder, Cu powder and Al powder18B4O33The quality and purity of the whisker powder are all99 to 99.9 percent.
Claims (2)
1. Al (aluminum)18B4O33The whisker reinforced silver-copper composite solder is characterized in that: according to the mass percentage, the alloy consists of 60-70% of Ag powder, 20-30% of Cu powder and 5-15% of Al18B4O33And (5) preparing the whisker.
2. Al according to claim 118B4O33The preparation method of the whisker reinforced silver-copper composite solder is characterized by comprising the following steps:
step 1, weighing 60-70% of Ag powder, 20-30% of Cu powder and 5-15% of Al powder according to mass percentage18B4O33Whisker, mixing to obtain original solder powder;
step 2, placing the original brazing filler metal powder and the grinding balls obtained in the step 1 into a planetary ball milling tank, vacuumizing, then filling argon into the ball milling tank, and carrying out ball milling for 2-8 hours at the rotating speed of 100-150 r/min to obtain Al18B4O33The crystal whisker reinforced silver-copper composite solder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810004388.0A CN108115308B (en) | 2018-01-03 | 2018-01-03 | Al (aluminum)18B4O33Whisker reinforced silver-copper composite solder and preparation method thereof |
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| CN201810004388.0A CN108115308B (en) | 2018-01-03 | 2018-01-03 | Al (aluminum)18B4O33Whisker reinforced silver-copper composite solder and preparation method thereof |
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| CN108115308B true CN108115308B (en) | 2020-06-19 |
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| CN113880426A (en) * | 2021-11-11 | 2022-01-04 | 广东省科学院新材料研究所 | Microcrystalline glass brazing filler metal for ceramic connection, preparation method thereof and ceramic connection method |
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| CN102211260A (en) * | 2011-05-25 | 2011-10-12 | 哈尔滨工业大学 | Ceramic phase reinforced copper-based composite solder and preparation method thereof |
| CN102240866A (en) * | 2011-05-19 | 2011-11-16 | 哈尔滨工业大学 | Aluminum borate crystal whisker reinforced low-temperature unleaded composite soldering paste and preparation method thereof |
| CN102699572A (en) * | 2012-06-21 | 2012-10-03 | 哈尔滨工业大学 | Nano particle reinforced Ag-base composite brazing filler metal and preparation method thereof |
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- 2018-01-03 CN CN201810004388.0A patent/CN108115308B/en active Active
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|---|---|---|---|---|
| CN1513812A (en) * | 2003-06-26 | 2004-07-21 | 哈尔滨工业大学 | Ceramic particle reinforced composite brazing alloy used for ceramic soldering |
| CN1544196A (en) * | 2003-11-17 | 2004-11-10 | 哈尔滨工业大学 | Mechanical alloying preparation method of ceramic grain reinforced composite solder |
| CN1792531A (en) * | 2005-12-30 | 2006-06-28 | 哈尔滨工业大学 | Filling composite welding flux vibrating liquid phase welding method for non-continuous strengthening aluminium base composite material |
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