CN112719690A - Composite brazing filler metal and preparation method thereof - Google Patents
Composite brazing filler metal and preparation method thereof Download PDFInfo
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- CN112719690A CN112719690A CN202110007304.0A CN202110007304A CN112719690A CN 112719690 A CN112719690 A CN 112719690A CN 202110007304 A CN202110007304 A CN 202110007304A CN 112719690 A CN112719690 A CN 112719690A
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000005219 brazing Methods 0.000 title claims abstract description 26
- 239000000945 filler Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006263 metalation reaction Methods 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 94
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- 229910000679 solder Inorganic materials 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910017944 Ag—Cu Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 17
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229940078494 nickel acetate Drugs 0.000 claims description 15
- JCYCCXPTYNHDRV-UHFFFAOYSA-N [Ni].OCCO Chemical compound [Ni].OCCO JCYCCXPTYNHDRV-UHFFFAOYSA-N 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 239000013522 chelant Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 239000002135 nanosheet Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- -1 nickel nanoparticle-modified graphite powder Chemical class 0.000 claims 3
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- 229910000669 Chrome steel Inorganic materials 0.000 claims 1
- 210000001161 mammalian embryo Anatomy 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 15
- 238000005245 sintering Methods 0.000 abstract description 10
- 238000003825 pressing Methods 0.000 abstract description 6
- 150000004703 alkoxides Chemical class 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 15
- 239000011812 mixed powder Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 5
- 239000002064 nanoplatelet Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910020220 Pb—Sn Inorganic materials 0.000 description 1
- 229910020816 Sn Pb Inorganic materials 0.000 description 1
- 229910020922 Sn-Pb Inorganic materials 0.000 description 1
- 229910008783 Sn—Pb Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a composite solder and a preparation method thereof, which comprises the steps of preparing graphene modified by nickel nanoparticles by a metal alkoxide method; the nickel nanoparticle modified graphene reinforced composite solder is prepared by adopting the processes of mechanical powder mixing, pressing, sintering and the like. The brazing filler metal comprises 0.3-3.5 wt.% of Ag, 0.1-1.0 wt.% of Cu, 0.01-0.5 wt.% of nickel nanoparticle modified graphite (Ni-GNSs), and the balance of Sn. According to the invention, the self-made nickel nanoparticle modified graphene is used as a reinforcing material, so that the bonding strength of the graphene and the brazing filler metal matrix interface is increased, and the strength of the brazing filler metal is improved.
Description
Technical Field
The invention relates to the field of brazing, in particular to a composite brazing filler metal and a preparation method thereof.
Background
The Sn-Pb solder has the advantages of low cost, low melting point, good wettability and the like, and is widely applied to electronic micro-connection, but with the enhancement of global environmental awareness, the international society of European Union and the like strongly prohibits the application of Pb in the electronic industry. Among many lead-free solders, Sn-Ag-Cu is considered to be the best alternative to traditional Pb-Sn solders in the electronics industry due to its superior properties. For example eutectic Sn-Ag-Cu solders are favored in surface mount technology and ball grid array packaging technology.
With the development of electronic devices toward fine pitch and high density, the reliability requirements of Sn-Ag-Cu solder joints are undoubtedly higher and higher. Graphene is considered to be an excellent strengthening phase of the Sn-Ag-Cu solder because of its extremely high specific surface area, excellent electrical conductivity and good toughness. However, due to the fact that the density difference between the graphene and the brazing filler metal matrix is large, and the graphene nanosheets have the agglomeration problem, the graphene and the brazing filler metal are unevenly distributed in the matrix brazing filler metal; in addition, the bonding strength of graphene and the matrix is poor, so that the load transmission between the brazing filler metal matrix and the strengthening phase is not uniform, and a good strengthening effect cannot be achieved. Therefore, it is required to optimize the performance of graphene to improve the distribution uniformity in the solder matrix and the interface bonding strength of graphene and the matrix.
Disclosure of Invention
The invention aims to provide a composite solder and a preparation method thereof, which can optimize the performance of graphene by improving the distribution uniformity in a solder matrix and the interface bonding strength of the graphene and the matrix.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a composite braze, comprising: ag. Cu, Sn and nickel nanoparticle modified graphene nanoplatelets, which are expressed as Ni-GNSs.
Preferably, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.3-3.5 wt.%, Cu: 0.1-1.0 wt.%, Ni-GNSs: 0.01-0.5 wt.%, and the balance of Sn.
The preparation method of the composite solder is characterized by comprising the following steps:
s1: uniformly dispersing graphene oxide in an ethylene glycol solution;
s2: further adding nickel acetate to obtain a nickel-ethylene glycol chelate/graphene oxide precursor;
s3: calcining the precursor prepared in the step S2 in a hydrogen atmosphere to prepare the nickel nanoparticle modified graphene;
s4: mixing Sn-Ag-Cu alloy powder serving as a matrix material with nickel nanoparticle modified graphite powder prepared by S3;
s5: adding agate balls into the powder obtained in the step S4, and pouring absolute alcohol into the powder to mix the powder;
s6: drying the powder uniformly mixed in the step S5, putting the dried powder into a chromium steel die with the diameter of 10 mm, and cold-pressing the dried powder into a blank under a universal testing machine at the pressure of 300-500 MPa;
s7: and sintering the blank prepared by the step S6 at 180 ℃ for 2-3 hours in an argon atmosphere, and taking out after cooling to room temperature to obtain the nickel nanoparticle modified graphene composite solder.
Preferably, the mass-to-volume ratio of the graphene oxide to the ethylene glycol solution is 1:2mg/mL, and the graphene oxide is subjected to ultrasonic treatment for more than 4 hours by using an ultrasonic cleaning machine, or is subjected to ultrasonic treatment for more than 20 minutes by using an ultrasonic cell disruption instrument.
Preferably, the molar volume ratio of the nickel acetate to the mixed solution in the S1 is 1:20 mmol/mL, the mixed solution is placed on a magnetic stirrer with a constant-temperature heating sleeve to be fully stirred and dissolved, and then the mixed solution is heated at the temperature of 145-165 ℃ for 0.5-2 hours and then is kept stand to room temperature, so that the nickel-ethylene glycol chelate/graphene oxide precursor is obtained.
Preferably, the hydrogen atmosphere in the S3 is 5% -10% of hydrogen-argon mixed gas.
Preferably, the nickel-ethylene glycol chelate/graphene oxide precursor is calcined at 500 ℃ for 2 hours, cooled to room temperature along with a furnace, and taken out to obtain the nickel nanoparticle modified graphene nanosheet.
Preferably, the particle size of the Sn-Ag-Cu alloy powder is 5-60 mu m.
Preferably, the Sn-Ag-Cu alloy powder is composed of, by mass: 0.3-3.5 wt.%, Cu: 0.1-1.0 wt.%, Ni-GNSs: 0.01-0.5 wt.%, and the balance of Sn.
Preferably, the mass fraction of the nickel nanoparticle modified graphene in S4 is 0.03-0.07 wt.%.
Compared with the prior art, the method improves the distribution uniformity in the solder matrix and the interface bonding strength of the graphene/Sn-Ag-Cu matrix by optimizing the performance of the graphene, and solves the problem of non-wetting between the graphene and the solder matrix. The self-made nickel nanoparticle modified graphene nanosheet is selected as a reinforcing material, so that the graphene in the prepared brazing filler metal is uniformly distributed, the bonding strength of the graphene and a brazing filler metal matrix interface is increased, and the strength of the brazing filler metal is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
In the drawings:
FIG. 1 is an SEM photograph of a nickel nanoparticle modified graphene nanosheet obtained by heating a mixed solution of nickel acetate, graphene oxide and ethylene glycol at 150 ℃ for 1 hour to react and sintering at 500 ℃ for 2 hours;
FIG. 2 is an XRD diffraction pattern of graphene oxide raw material and nickel nanoparticle modified graphene nanoplatelets;
FIG. 3 is an SEM photograph of a nickel nanoparticle modified graphene nanosheet obtained by heating a mixed solution of nickel acetate, graphene oxide and ethylene glycol at 155 ℃ for 1 hour to react and sintering at 500 ℃ for 2 hours.
Detailed Description
The present invention is to overcome the defects of the prior art, and provides a composite solder and a preparation method thereof, which are further described in detail with reference to the following examples.
The invention provides a composite brazing filler metal, which is characterized by comprising: ag. Cu, Ni-GNSs and Sn. The Ni-GNSs, namely the graphene nanosheets modified by the nickel nanoparticles, are prepared by a metal alkoxide method and serve as a reinforcing material, so that the bonding strength of the graphene and a brazing filler metal matrix interface is increased, and the strength of the brazing filler metal is improved.
In the application, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.3-3.5 wt.%, Cu: 0.1-1.0 wt.%, Ni-GNSs: 0.01-0.5 wt.%, and the balance of Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.3 wt.%, Cu: 0.5 wt.%, Ni-GNSs: 0.01wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 3.5 wt.%, Cu: 0.6 wt.%, Ni-GNSs: 0.01wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.5 wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.25 wt.%, Cu: 0.65 wt.%, Ni-GNSs: 0.1 wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.07wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 3.5 wt.%, Cu: 0.5 wt.%, Ni-GNSs: 0.05wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 3.0 wt.%, Cu: 0.5 wt.%, Ni-GNSs: 0.05wt.%, with the balance being Sn.
In one embodiment of the invention, the mass fractions of Ag, Cu, Ni-GNSs and Sn are Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.03 wt.%, with the balance being Sn.
The preparation method of the composite solder is characterized by comprising the following steps:
s1: uniformly dispersing graphene oxide in an ethylene glycol solution;
s2: further adding nickel acetate to obtain a nickel-ethylene glycol chelate/graphene oxide precursor;
s3: calcining the precursor prepared by the step S2 in a hydrogen atmosphere to prepare the nickel nanoparticle modified graphene,
s4: mixing Sn-Ag-Cu alloy powder serving as a matrix material with nickel nanoparticle modified graphite powder prepared by S3;
s5: adding agate balls into the powder obtained in the step S4, and pouring absolute alcohol into the powder to mix the powder;
s6: drying the powder uniformly mixed in the step S5, putting the dried powder into a chromium steel die with the diameter of 10 mm, and cold-pressing the dried powder into a blank under a universal testing machine at the pressure of 300-500 MPa;
s7: and sintering the blank prepared by the step S6 at 180 ℃ for 2-3 hours in an argon atmosphere, and taking out after cooling to room temperature to obtain the nickel nanoparticle modified graphene composite solder.
In step S1, the mass-to-volume ratio of the graphene oxide to the ethylene glycol solution is 1:2mg/mL, and the mixed solution of the graphene oxide and the ethylene glycol solution is subjected to ultrasound in an ultrasonic cleaning machine for 4 hours, wherein the ultrasonic cleaning machine is changed to water every hour to prevent the ultrasonic temperature from being too high for a long time. In a preferred embodiment of the present invention, graphene oxide may be dispersed in an ultrasonic cell disruptor, and the ultrasound may be performed for 20 minutes by using a spaced ultrasound method.
In one embodiment of the invention, the molar volume ratio of the nickel acetate to the mixed solution in the S1 is 1:20 mmol/mL, the mixed solution is placed on a magnetic stirrer with a constant-temperature heating sleeve to be fully stirred and dissolved, and then the mixed solution is heated at the temperature of 145-165 ℃ for 0.5-2 hours and then is kept standing to the room temperature. The magnetic stirring is carried out while the temperature is kept during the heating process. And then cleaning the substrate for 3-4 times by using alcohol to obtain a nickel-ethylene glycol chelate/graphene oxide (Co-glycollate/GONSs) precursor. The magnetic stirrer is preferably heated at 145 ℃ for 2 hours, preferably at 150 ℃ for 1 hour, preferably at 155 ℃ for 1 hour, preferably at 165 ℃ for 0.5 hour.
In an embodiment of the invention, the precursor obtained in the step S2 is placed in a tube furnace, calcined at 500 ℃ for 2 hours in a hydrogen atmosphere, cooled to room temperature along with the furnace, and taken out, so as to prepare the nickel nanoparticle modified graphene nanoplatelets (Ni-GNSs), wherein the hydrogen atmosphere is 5% -10% of hydrogen-argon mixed gas. The purity of the gas is more than 99.9 percent, and the gas is continuously introduced in the heating, heat preservation and cooling processes. The hydrogen atmosphere accounts for preferably 5%, 8% and 10%.
In step S4, the Sn-Ag-Cu alloy powder has a particle size of 5-60 μm, preferably a powder diameter range of 5-10 μm. The metal powder particle size is a range, and metal powder particles of a single particle size are not used in this application.
In the present invention, an appropriate amount of Ni-GNSs is taken as a strengthening phase and is fully mixed with Sn-Ag-Cu matrix powder. The components are Ag: 0.3-3.5 wt.%, Cu: 0.1-1.0 wt.%, Ni-GNSs: 0.01-0.5 wt.%, and the balance of Sn. The mixed powder adopts mechanical mixed powder and star-shaped ball milling mixed powder. The mechanical powder mixing process comprises the following steps: adding agate balls into the mixed powder, pouring absolute alcohol, mixing at a rotating speed of 150-200 r/min for 20 hours, and paying attention to supplement the absolute alcohol in the powder mixing process. The star-type powder mixing process comprises the following steps: adding agate balls into the mixed powder, pouring anhydrous alcohol with the content of anhydrous alcohol being less than that of the mixed powder and the agate balls, and mixing for 10 hours at the rotating speed of 180 r/min. And then placing the powder in a vacuum drying oven, vacuumizing to 0.1 MPa, and preserving heat for 5 hours at 35 ℃ to obtain the uniformly mixed composite brazing filler metal powder.
In an embodiment of the invention, the mixed solution of nickel acetate, graphene oxide and ethylene glycol is heated at 150 ℃ for 1 hour to react, and then is allowed to stand to room temperature, so as to obtain the nickel-ethylene glycol chelate/graphene oxide precursor.
Preferably, the mass fraction of the nickel nanoparticle modified graphene in S4 is 0.03-0.07 wt.%.
Example 1
A composite braze, comprising: ag. Cu, Sn and nickel nanoparticle modified graphene nanoplatelets, which are expressed as Ni-GNSs. The mass fractions of the Ag, the Cu, the Ni-GNSs and the Sn are Ag: 3.0 wt.%, Cu: 0.5 wt.%, Ni-GNSs: 0.05wt.%, with the balance being Sn.
Example 2
A composite braze, comprising: ag. Cu, Sn and nickel nanoparticle modified graphene nanoplatelets, which are expressed as Ni-GNSs. The mass fractions of the Ag, the Cu, the Ni-GNSs and the Sn are Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.03 wt.%, with the balance being Sn.
Example 3
The preparation method of the composite solder is characterized by comprising the following steps:
s1: uniformly dispersing graphene oxide in an ethylene glycol solution; the mass volume ratio of the graphene oxide to the glycol solution is 1:2mg/mL, and the mixed solution of the graphene oxide and the glycol solution is subjected to ultrasonic treatment in an ultrasonic cleaning machine for 4 hours, wherein the ultrasonic cleaning machine is used for replacing water once per hour in order to prevent overhigh ultrasonic temperature for a long time;
s2: further adding nickel acetate, wherein the molar volume ratio of the nickel acetate to the mixed solution in the S1 is 1:20 mmol/mL, placing the mixture on a magnetic stirrer with a constant-temperature heating sleeve, fully stirring and dissolving the mixture, heating the mixture at 165 ℃ for 0.5 hour, standing the mixture to room temperature, carrying out heat preservation and magnetic stirring in the heating process, and then washing the mixture for 3-4 times by using alcohol to obtain a nickel-ethylene glycol chelate/graphene oxide (Co-glycollate/GONSs) precursor;
s3: calcining the precursor prepared in the step S2 at 500 ℃ for 2 hours in a hydrogen atmosphere, cooling the calcined precursor to room temperature along with a furnace, and taking out the calcined precursor to prepare the nickel nanoparticle modified graphene, wherein the hydrogen atmosphere is 5% of hydrogen-argon mixed gas;
s4: mixing Sn-Ag-Cu alloy powder serving as a matrix material with nickel nanoparticle modified graphite powder prepared by S3; the alloy powder has the particle size of 5-60 mu m, and the mass fraction is Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.03 wt.%, balance Sn
S5: and (5) mixing the powder in the step (S4), wherein the mechanical powder mixing is adopted for mixed powder mixing, and the process is as follows: adding agate balls into the mixed powder, pouring anhydrous alcohol, mixing at the rotating speed of 150 r/min for 20 hours, supplementing the anhydrous alcohol in the powder mixing process, then placing the powder in a vacuum drying oven, vacuumizing to 0.1 MPa, and preserving heat at 35 ℃ for 5 hours to obtain uniformly mixed composite solder powder;
s6: drying the powder uniformly mixed in the step S5, putting the dried powder into a chromium steel die with the diameter of 10 mm, and cold-pressing the die into a blank under a universal testing machine at the pressure of 300 MPa;
s7: and sintering the blank prepared by the step S6 in an argon atmosphere at 180 ℃ for 3 hours, cooling to room temperature, and taking out to obtain the nickel nanoparticle modified graphene composite solder, wherein the hydrogen atmosphere is 5% of hydrogen-argon mixed gas.
Example 4
The preparation method of the composite solder is characterized by comprising the following steps:
s1: uniformly dispersing graphene oxide in an ethylene glycol solution; the mass-to-volume ratio of the graphene oxide to the glycol solution is 1:2mg/mL, the graphene oxide is dispersed in an ultrasonic cell disruption instrument, and ultrasonic treatment is carried out for 20 minutes in an interval ultrasonic mode;
s2: further adding nickel acetate, wherein the molar volume ratio of the nickel acetate to the mixed solution in the S1 is 1:20 mmol/mL, placing the mixture on a magnetic stirrer with a constant-temperature heating sleeve, fully stirring and dissolving, heating the mixture at 150 ℃ for 1 hour, standing the mixture to room temperature, carrying out heat preservation and magnetic stirring in the heating process, and then washing the mixture for 3-4 times by using alcohol to obtain a nickel-ethylene glycol chelate/graphene oxide (Co-glycollate/GONSs) precursor;
s3: calcining the precursor prepared in the step S2 at 500 ℃ for 2 hours in a hydrogen atmosphere, cooling the calcined precursor to room temperature along with a furnace, and taking out the calcined precursor to prepare the nickel nanoparticle modified graphene, wherein the hydrogen atmosphere is 10% of hydrogen-argon mixed gas;
s4: mixing Sn-Ag-Cu alloy powder serving as a matrix material with nickel nanoparticle modified graphite powder prepared by S3; the alloy powder has the particle size of 5-10 mu m, and the mass fraction is Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.03 wt.%, with the balance being Sn.
S5: and (5) mixing the powder in the step (S4), wherein the star-type powder mixing is adopted for mixed powder mixing, and the process is as follows: adding agate balls into the mixed powder, pouring absolute alcohol, mixing the mixed powder and the agate balls at a rotating speed of 180r/min for 10 hours, then placing the mixture in a vacuum drying oven, vacuumizing to 0.1 MPa, and preserving heat at 35 ℃ for 5 hours to obtain uniformly mixed composite solder powder;
s6: drying the powder uniformly mixed in the step S5, putting the dried powder into a chromium steel die with the diameter of 10 mm, and cold-pressing the die into a blank under a universal testing machine at the pressure of 400 MPa;
s7: and sintering the blank prepared by the step S6 in an argon atmosphere at 180 ℃ for 3 hours, cooling to room temperature, and taking out to obtain the nickel nanoparticle modified graphene composite solder, wherein the hydrogen atmosphere is 10% of hydrogen-argon mixed gas.
Example 5
The preparation method of the composite solder is characterized by comprising the following steps:
s1: uniformly dispersing graphene oxide in an ethylene glycol solution; the mass-to-volume ratio of the graphene oxide to the glycol solution is 1:2mg/mL, the graphene oxide is dispersed in an ultrasonic cell disruption instrument, and ultrasonic treatment is carried out for 20 minutes in an interval ultrasonic mode;
s2: further adding nickel acetate, wherein the molar volume ratio of the nickel acetate to the mixed solution in the S1 is 1:20 mmol/mL, placing the mixture on a magnetic stirrer with a constant-temperature heating sleeve, fully stirring and dissolving the mixture, heating the mixture at 155 ℃ for 1 hour, standing the mixture to room temperature, carrying out magnetic stirring while keeping the temperature in the heating process, and then washing the mixture for 3-4 times by using alcohol to obtain a nickel-ethylene glycol chelate/graphene oxide (Co-glycollate/GONSs) precursor;
s3: calcining the precursor prepared in the step S2 in a hydrogen atmosphere at 500 ℃ for 2 hours, cooling the calcined precursor to room temperature along with a furnace, and taking out the calcined precursor to prepare the nickel nanoparticle modified graphene, wherein the hydrogen atmosphere is 7% of hydrogen-argon mixed gas;
s4: mixing Sn-Ag-Cu alloy powder serving as a matrix material with nickel nanoparticle modified graphite powder prepared by S3; the alloy powder has the particle size of 5-10 mu m, and the mass fraction is Ag: 0.3 wt.%, Cu: 0.7 wt.%, Ni-GNSs: 0.01wt.%, with the balance being Sn.
S5: and (5) mixing the powder in the step (S4), wherein the mechanical powder mixing is adopted for mixed powder mixing, and the process is as follows: adding agate balls into the mixed powder, pouring anhydrous alcohol, mixing at the rotating speed of 200 r/min for 20 hours, supplementing the anhydrous alcohol in the powder mixing process, then placing the powder in a vacuum drying oven, vacuumizing to 0.1 MPa, and preserving heat at 35 ℃ for 5 hours to obtain uniformly mixed composite solder powder;
s6: drying the powder uniformly mixed in the step S5, putting the dried powder into a chromium steel die with the diameter of 10 mm, and cold-pressing the die into a blank under a universal testing machine at the pressure of 500 MPa;
s7: and sintering the blank prepared by the step S6 at 180 ℃ for 2 hours in an argon atmosphere, cooling to room temperature, and taking out to obtain the nickel nanoparticle modified graphene composite solder, wherein the hydrogen atmosphere is 7% of hydrogen-argon mixed gas.
Examples of the experiments
As can be seen from fig. 1 and 3, the nickel-ethylene glycol chelate/graphene oxide precursor obtained by heating at 150 ℃ for 1 hour for reaction, the nickel nanoparticle modified graphene nanosheet obtained by sintering at 500 ℃ for 2 hours, is smoother in surface, finer in nickel nanoparticles and uniform in distribution, compared to the nickel-ethylene glycol chelate/graphene oxide precursor obtained by heating at 155 ℃ for 1 hour for reaction, and the nickel nanoparticle modified graphene nanosheet obtained by sintering at 500 ℃ for 2 hours.
As can be seen from fig. 2, in the 2 θ normal scanning mode, the diffraction peak of the raw material is the diffraction peak of graphene oxide (lower curve in fig. 2); in the graphene modified by the nickel nanoparticles prepared by the metal alkoxide method, the diffraction peak of graphene oxide disappears, the graphene oxide is reduced into reduced graphene oxide by hydrogen, and the rest diffraction peaks completely correspond to standard cards JCPDS NO.04-0850 of the nickel simple substance (the upper curve of FIG. 2).
Claims (10)
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