CN112719690A - Composite brazing filler metal and preparation method thereof - Google Patents
Composite brazing filler metal and preparation method thereof Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- nickel
- powder
- graphene
- composite solder
- gnss
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
Landscapes
- 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)
1. A composite braze, comprising: ag. Cu, Sn and nickel nanoparticle modified graphene nanoplatelets, which are expressed as Ni-GNSs.
2. The composite solder according to claim 1, wherein 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.
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;
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.
4. The composite solder according to claim 3, wherein the mass-to-volume ratio of the graphene oxide to the glycol solution is 1:2mg/mL, and the graphene oxide and the glycol solution are subjected to ultrasonic treatment for more than 4 hours by using an ultrasonic cleaning machine or more than 20 minutes by using an ultrasonic cell disruptor.
5. The composite solder as claimed in claim 4, wherein the molar volume ratio of the nickel acetate to the mixed solution in S1 is 1:20 mmol/mL, the mixed solution is placed on a magnetic stirrer with a constant-temperature heating jacket 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 placed to room temperature to obtain the nickel-ethylene glycol chelate/graphene oxide precursor.
6. The composite solder according to claim 5, wherein the hydrogen atmosphere in S3 is 5-10% of hydrogen-argon mixed gas.
7. The composite solder as claimed in claim 6, wherein 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.
8. The composite solder according to claim 7, wherein the particle size of the Sn-Ag-Cu alloy powder is 5-60 μm.
9. The composite solder according to claim 8, wherein 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.
10. The composite solder as claimed in claim 9, wherein the mass fraction of the nickel nanoparticle modified graphene in the S4 is 0.03-0.076 wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110007304.0A CN112719690A (en) | 2021-01-05 | 2021-01-05 | Composite brazing filler metal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110007304.0A CN112719690A (en) | 2021-01-05 | 2021-01-05 | Composite brazing filler metal and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112719690A true CN112719690A (en) | 2021-04-30 |
Family
ID=75591390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110007304.0A Pending CN112719690A (en) | 2021-01-05 | 2021-01-05 | Composite brazing filler metal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112719690A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114082970A (en) * | 2021-12-06 | 2022-02-25 | 重庆科技学院 | Preparation method of metal nanoparticle modified carbon-based nanomaterial, modified composite solder and preparation method of modified composite solder |
| CN114414333A (en) * | 2022-01-10 | 2022-04-29 | 湘潭大学 | Preparation method and application of rare earth modified graphene oxide composite solder |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102581504A (en) * | 2012-03-23 | 2012-07-18 | 天津大学 | Graphene reinforced lead-free solder and preparation method thereof |
| JP2013018010A (en) * | 2011-07-07 | 2013-01-31 | Fuji Electric Co Ltd | Lead-free solder |
| CN105171277A (en) * | 2015-09-25 | 2015-12-23 | 天津大学 | Preparation method of tin-based silver graphene lead-free composite solder |
| CN105838913A (en) * | 2016-04-08 | 2016-08-10 | 上海和伍复合材料有限公司 | Graphene/nickel composite material and preparation method thereof |
| CN108817727A (en) * | 2018-07-19 | 2018-11-16 | 河南科技大学 | Pyrolysismethod synthesis is by force in conjunction with the high-strength Sn-Ag-Cu-RE system composite soldering and preparation method of the enhancing of copper-plated graphite alkene |
| CN109378455A (en) * | 2018-10-08 | 2019-02-22 | 西安交通大学 | A kind of classifying porous cobalt oxide nanosphere/graphene composite material and preparation method thereof |
| CN110936061A (en) * | 2019-12-20 | 2020-03-31 | 重庆科技学院 | Low-silver SAC composite solder with high tensile strength |
-
2021
- 2021-01-05 CN CN202110007304.0A patent/CN112719690A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013018010A (en) * | 2011-07-07 | 2013-01-31 | Fuji Electric Co Ltd | Lead-free solder |
| CN102581504A (en) * | 2012-03-23 | 2012-07-18 | 天津大学 | Graphene reinforced lead-free solder and preparation method thereof |
| CN105171277A (en) * | 2015-09-25 | 2015-12-23 | 天津大学 | Preparation method of tin-based silver graphene lead-free composite solder |
| WO2017050284A1 (en) * | 2015-09-25 | 2017-03-30 | 天津大学 | Preparation method for tin-based silver graphene lead-free composite solder |
| CN105838913A (en) * | 2016-04-08 | 2016-08-10 | 上海和伍复合材料有限公司 | Graphene/nickel composite material and preparation method thereof |
| CN108817727A (en) * | 2018-07-19 | 2018-11-16 | 河南科技大学 | Pyrolysismethod synthesis is by force in conjunction with the high-strength Sn-Ag-Cu-RE system composite soldering and preparation method of the enhancing of copper-plated graphite alkene |
| CN109378455A (en) * | 2018-10-08 | 2019-02-22 | 西安交通大学 | A kind of classifying porous cobalt oxide nanosphere/graphene composite material and preparation method thereof |
| CN110936061A (en) * | 2019-12-20 | 2020-03-31 | 重庆科技学院 | Low-silver SAC composite solder with high tensile strength |
Non-Patent Citations (4)
| Title |
|---|
| GUANG CHEN等: "Microstructures and properties of new Sn-Ag-Cu lead-free solder reinforced with Ni-coated graphene nanosheets", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 姚彦馨: "三明治状钴基氧化物/rGO负极材料的制备及其电化学性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
| 王悔改等: "微连接用碳基纳米颗粒增强无铅复合钎料的研究新进展", 《材料热处理学报》 * |
| 程婕: "《电子产品制造工程实践技术》", 31 August 2015, 西北工业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114082970A (en) * | 2021-12-06 | 2022-02-25 | 重庆科技学院 | Preparation method of metal nanoparticle modified carbon-based nanomaterial, modified composite solder and preparation method of modified composite solder |
| CN114414333A (en) * | 2022-01-10 | 2022-04-29 | 湘潭大学 | Preparation method and application of rare earth modified graphene oxide composite solder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112719690A (en) | Composite brazing filler metal and preparation method thereof | |
| WO2017050284A1 (en) | Preparation method for tin-based silver graphene lead-free composite solder | |
| CN101121972A (en) | Method for preparing Mo-Cu composite material | |
| CN106799496B (en) | A kind of graphite and alusil alloy composite electron encapsulating material and preparation method thereof | |
| JP6855539B2 (en) | Sintered paste composition for power semiconductor bonding | |
| CN106521203B (en) | A kind of preparation method of AgCuTi alloys, preparation method of its foil solder and products thereof | |
| CN108817727A (en) | Pyrolysismethod synthesis is by force in conjunction with the high-strength Sn-Ag-Cu-RE system composite soldering and preparation method of the enhancing of copper-plated graphite alkene | |
| CN114799616B (en) | High-entropy intermetallic compound material, preparation method thereof and electronic solder | |
| Gui et al. | Interfacial reaction, wettability, and shear strength of ultrasonic-assisted lead-free solder joints prepared using Cu–GNSs-doped flux | |
| CN107009044B (en) | A kind of lead-free solder and preparation method thereof | |
| Lu et al. | Structure and properties of low-Ag SAC solders for electronic packaging | |
| CN110666267B (en) | Tin soldering point alloying forming method | |
| CN109609805B (en) | Preparation process of carbon-based nano-material reinforced low-melting-point composite material | |
| Chen et al. | Retained ratio of reinforcement in SAC305 composite solder joints: effect of reinforcement type, processing and reflow cycle | |
| CN113070604B (en) | Double-layer solder sheet and preparation process thereof | |
| CN108823444B (en) | Short-process preparation method of copper-carbon composite material | |
| CN113977133A (en) | Corrosion-resistant composite brazing filler metal for copper-aluminum transition wire clamp and preparation method thereof | |
| CN107009045B (en) | A kind of Sn-Bi system used for electronic packaging composite soldering and preparation method thereof | |
| CN115846672A (en) | Preparation method of high-strength high-conductivity copper-based composite material for lead frame | |
| CN114082970A (en) | Preparation method of metal nanoparticle modified carbon-based nanomaterial, modified composite solder and preparation method of modified composite solder | |
| CN114871626A (en) | Tin-silver-copper brazing filler metal | |
| CN115430949A (en) | Five-membered eutectic high-toughness low-temperature tin-bismuth series solder and preparation method thereof | |
| Yang et al. | Comparison between bulk and particle solder alloy on the performance of low-melting solder joints | |
| CN114985750B (en) | Preparation method of tin-silver-copper alloy nano powder, tin-silver-copper nano alloy low-temperature slurry, preparation method and application thereof | |
| CN110936061A (en) | Low-silver SAC composite solder with high tensile strength |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |