CN113977133A - Corrosion-resistant composite brazing filler metal for copper-aluminum transition wire clamp and preparation method thereof - Google Patents
Corrosion-resistant composite brazing filler metal for copper-aluminum transition wire clamp and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 73
- 239000002184 metal Substances 0.000 title claims abstract description 73
- 238000005260 corrosion Methods 0.000 title claims abstract description 58
- 230000007797 corrosion Effects 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000007704 transition Effects 0.000 title claims abstract description 43
- 238000005219 brazing Methods 0.000 title claims abstract description 42
- 239000000945 filler Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 93
- 229910000679 solder Inorganic materials 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000007731 hot pressing Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000009736 wetting Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000005496 eutectics Effects 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910007570 Zn-Al Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018563 CuAl2 Inorganic materials 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005258 corrosion kinetic Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
- B23K35/282—Zn 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
- H01R4/62—Connections between conductors of different materials; Connections between or with aluminium or steel-core aluminium conductors
- H01R4/625—Soldered or welded connections
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/12—Copper or alloys thereof
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a corrosion-resistant composite solder for a copper-aluminum transition wire clamp and a preparation method thereof, wherein the composite solder comprises the following raw materials in percentage by weight: 10-22% of Al, 0.3-0.6% of Ag, 0.4-1% of Cu, 0.05-0.2% of rare earth elements, 0.01-0.12% of graphene and the balance of Zn. The preparation method of the brazing filler metal mainly comprises the steps of crushing graphene into powder, uniformly mixing the powder with metal powder, sintering the uniformly mixed mixture of the metal raw material and the graphene powder at a high temperature by a vacuum hot pressing sintering method, and cooling to room temperature after sintering is finished to obtain the corrosion-resistant composite brazing filler metal. The corrosion-resistant composite solder obtained by the invention is added with a proper amount of graphene, the eutectic structure proportion is increased, and the crystal grains of the solder are refined, so that the wetting spreadability and the tensile strength of the solder are improved, a laminated structure is formed by vacuum hot-pressing sintering between the graphene and the metal in the solder, the entry of corrosive media such as water, oxygen and the like is blocked, and the corrosion resistance of the composite solder is improved.
Description
Technical Field
The invention belongs to the technical field of brazing filler metal materials, and particularly relates to a corrosion-resistant composite brazing filler metal for a copper-aluminum transition wire clamp and a preparation method thereof.
Background
The graphene is formed by sp carbon atoms2The basic structural unit of the hybrid-connected monoatomic layer is the most stable benzene six-membered ring in the organic material, the theoretical thickness of the hybrid-connected monoatomic layer is only 0.35nm, and the hybrid-connected monoatomic layer is the thinnest two-dimensional material discovered at present. The graphene with the nano-scale thickness has unique physicochemical properties, for example, the strength of the graphene is the highest in tested materials, reaches 130GPa, and is more than 100 times that of steel; the carrier mobility of the material reaches 1.5 multiplied by 104cm2·V-1·s-12 times of the currently known indium antimonide material with the highest mobility, 10 times of the mobility of the commercial silicon wafer, and the mobility of the indium antimonide material can even reach 2.5 multiplied by 10 under specific conditions (such as low-temperature quenching and the like)5cm2·V-1·s-1(ii) a The thermal conductivity of the graphene can reach 5 multiplied by 103W·m-1·K-13 times as much as diamond; the graphene also has special properties such as super-strong corrosion resistance, room-temperature quantum Hall effect, room-temperature ferromagnetism and the like, and can be widely applied to the fields of nano materials, energy sources, biomedicine, electricity and the like.
In an electric energy conversion system, a plurality of copper and aluminum are connected, and a copper-aluminum transition wire clamp is used. The wire clamp is a typical copper-aluminum connecting device widely applied in the power industry. The copper-aluminum transition wire clamp is mainly used for connecting a bus down lead with an outlet terminal of electrical equipment, such as a transformer, a circuit breaker, a mutual inductor, an isolating switch, a wall bushing and the like. The copper-aluminum transition wire clamp is used, so that a plurality of problems of electric conduction, electrochemical corrosion and the like can be avoided, and the copper-aluminum transition wire clamp is an effective means for replacing copper with aluminum and saving copper materials, thereby reducing the cost of power transmission and transformation equipment.
The copper-aluminum transition wire clamp is generally used for connecting copper materials and aluminum materials in a brazing welding mode to realize effective and reliable copper-aluminum transition. However, the copper-aluminum transition wire clamp obtained by brazing can be affected by factors of working conditions and environments in long-term operation to form corrosion damage or stress damage, so that the wire clamp is aged and broken, and great hidden danger is caused to safe operation of equipment and a power grid. Therefore, the key for improving the stable operation capability of the copper-aluminum transition wire clamp is to solve the problems of poor corrosion performance and low strength of the brazing joint of the copper-aluminum transition wire clamp. The Zn-Al based solder is a mature solder applied in the brazing process, and is easy to corrode in the environment because the corrosion potentials of Zn element and Al element are relatively small. In the brazing process, the Zn-Al-based brazing filler metal and the copper substrate or the aluminum substrate are easy to react to form CuAl2Brittle phase, which affects the mechanical properties of the copper-aluminum transition wire clamp. In order to enhance the corrosion resistance of the Zn-Al-based brazing filler metal and improve the mechanical property of the copper-aluminum transition wire clamp, at present, a common method is to improve the corrosion resistance of the Zn-Al-based brazing filler metal by adjusting the mass ratio of Zn element to Al element in the Zn-Al-based brazing filler metal, but the method needs a large amount of experiments to screen out a proper data ratio, has large workload, is complicated to operate, has large experimental randomness and can generate large artificial errors, so that the probability of inaccuracy of experimental data is high. Therefore, the research on a novel corrosion-resistant Zn-Al-based brazing filler metal for a copper-aluminum transition wire clamp is a technical problem which needs to be solved continuously at present.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a corrosion-resistant composite solder for a copper-aluminum transition wire clamp and a preparation method thereof. The composite solder has good wettability, high tensile strength and strong corrosion resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following raw materials in percentage by weight: 10-22% of Al, 0.3-0.6% of Ag, 0.4-1% of Cu, 0.05-0.2% of rare earth elements, 0.01-0.12% of graphene and the balance of Zn.
Further, the graphene accounts for 0.01-0.09% by weight.
Further, the graphene is a graphene nano sheet, the thickness of the graphene nano sheet is 3-15nm, and the size of the graphene nano sheet is 3-10 μm.
Further, the graphene is prepared by reducing graphene oxide with hydrazine hydrate.
Further, the composite brazing filler metal is brazing filler metal in any shape of powder, strips, rods and sheets or a mixture of brazing filler metals in a plurality of shapes.
Further, the preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp is characterized by comprising the following steps of:
(1) weighing the raw materials of the composite solder in percentage by weight;
(2) firstly, crushing and dispersing the graphene weighed in the step (1) by using an ultrasonic cell crusher, and then fully mixing and centrifuging the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) and (4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at a high temperature by using a vacuum hot pressing sintering method, and cooling to room temperature after sintering to obtain the corrosion-resistant composite brazing filler metal.
Further, the diameter of the metal raw material powder of the step (2) is 10 to 100 μm.
Further, the sintering temperature of the vacuum hot-pressing sintering in the step (4) is 400--3-5×10-3Pa。
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a certain amount of Ag, Cu, rare earth elements and graphene are added on the basis of the traditional Zn-Al-based brazing filler metal, Ag is in limited mutual solubility with base metals Al and Cu when in a liquid state, and the spreadability and the fluidity of the Zn-Al-based brazing filler metal which can be improved by adding a proper amount of Ag are added, so that the brazing filler metal and the base metals fully react to better fill brazing seams, and meanwhile, the strength of a brazed joint can be improved by adding a proper amount of Ag; the Cu has high strength and melting point, is firstly solidified to form particles during crystallization, can improve the strength of a soldered joint by improving the strength of the solder, and simultaneously can improve the wettability of the solder to a copper matrix and reduce the dissolution of the copper matrix into the liquid solder; the rare earth element is an active element, the surface tension of the alloy can be reduced and the wetting and spreading performance of the brazing filler metal can be improved by adding a proper amount of the rare earth element, and the excessive addition of the rare earth element can form rare earth metal oxide, so that the spreadability of the brazing filler metal is poor; graphene is used as a core additive element, is a nanoscale strengthening phase, has high-temperature stability, corrosion resistance, excellent mechanical property and large specific surface area, and is added with a proper amount of graphene in the process of preparing the brazing filler metal to refine the grain structure of the brazing filler metal, increase the proportion of eutectic structures and refine the grains of the brazing filler metal, so that the wetting spreadability and tensile strength of the brazing filler metal are improved, the graphene and the metal in the brazing filler metal are sintered by vacuum hot pressing to form a laminated structure, the entry of corrosive media such as water, oxygen and the like is blocked, and the corrosion resistance of the composite brazing filler metal is improved; if excessive graphene and metal in the brazing filler metal are sintered in a vacuum hot pressing mode, due to the fact that the amount of the graphene is too large, sintering agglomeration is easy to cause, a laminated structure is difficult to form, corrosive media such as water and oxygen enter a welding line formed by the brazing filler metal through agglomerated gaps, and corrosion of the wire clamp is accelerated.
Detailed Description
The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The graphene nanosheets are all prepared by reducing graphene oxide with hydrazine hydrate, and the specific preparation method comprises the following steps: firstly, preparing graphene oxide into a solution, and adding hydrazine hydrate (the mass ratio of the graphene oxide to the hydrazine hydrate is 1:0.7-1:1) into the solution; then reducing in water bath at 90-95 deg.C for 1-2h, taking out, and filtering; and finally, putting the filtered solution into an oven at the temperature of 30-40 ℃ for drying for 36-40h, and taking out the dried solution to obtain the graphene nano-sheet.
Example 1
The corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following raw materials in percentage by weight: 10% of Al, 0.3% of Ag, 0.4% of Cu, 0.05% of rare earth elements, 0.01% of graphene and the balance of Zn.
The graphene is a graphene nano sheet with the thickness of 3nm and the size of 3 mu m,
the preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following steps:
(1) weighing the raw materials of the composite solder according to the weight percentage;
(2) firstly, crushing and dispersing the graphene nano sheets weighed in the step (1) by using an ultrasonic cell crusher, then fully mixing the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment, and centrifuging to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at a high temperature of 400 ℃ by using a vacuum hot pressing sintering method, wherein the sintering temperature is 30MPa, the sintering pressure is 30min, the sintering vacuum degree is 1 multiplied by 10-3Pa, cooling to room temperature after sintering to obtain the copper-aluminum alloy materialThe corrosion-resistant composite solder for the transition wire clamp is in the shape of any one or a mixture of powder, strips, rods and sheets.
Example 2
The corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following raw materials in percentage by weight: 13% of Al, 0.4% of Ag, 0.5% of Cu, 0.09% of rare earth elements, 0.03% of graphene and the balance of Zn. The graphene is a graphene nano sheet with the thickness of 5nm and the size of 5 mu m,
the preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following steps:
(1) weighing the raw materials of the composite solder according to the weight percentage;
(2) firstly, crushing and dispersing the graphene nano sheets weighed in the step (1) by using an ultrasonic cell crusher, then fully mixing the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment, and centrifuging to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at a high temperature of 410 ℃, a sintering pressure of 30MPa, a sintering time of 33min and a sintering vacuum degree of 2 x 10 by using a vacuum hot pressing sintering method-3Pa, cooling to room temperature after sintering to obtain the corrosion-resistant composite solder for the copper-aluminum transition wire clamp, wherein the shape of the obtained composite solder is any one or a mixture of powder, strips, rods and sheets.
Example 3
The corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following raw materials in percentage by weight: 16% of Al, 0.5% of Ag, 0.7% of Cu, 0.14% of rare earth elements, 0.06% of graphene and the balance of Zn. The graphene is a graphene nano sheet with the thickness of 10nm and the size of 7 mu m,
the preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following steps:
(1) weighing the raw materials of the composite solder according to the weight percentage;
(2) firstly, crushing and dispersing the graphene nano sheets weighed in the step (1) by using an ultrasonic cell crusher, then fully mixing the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment, and centrifuging to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at a high temperature of 420 ℃, the sintering pressure of 30MPa, the sintering time of 36min and the sintering vacuum degree of 3 x 10 by using a vacuum hot pressing sintering method-3Pa, cooling to room temperature after sintering to obtain the corrosion-resistant composite solder for the copper-aluminum transition wire clamp, wherein the shape of the obtained composite solder is any one or a mixture of powder, strips, rods and sheets.
Example 4
The corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following raw materials in percentage by weight: 19% of Al, 0.55% of Ag, 0.5% of Cu, 0.18% of rare earth elements, 0.09% of graphene and the balance of Zn. The graphene is a graphene nano sheet with the thickness of 12nm and the size of 8 mu m,
the preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following steps:
(1) weighing the raw materials of the composite solder according to the weight percentage;
(2) firstly, crushing and dispersing the graphene nano sheets weighed in the step (1) by using an ultrasonic cell crusher, then fully mixing the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment, and centrifuging to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at high temperature of 440 ℃, the sintering pressure of 30MPa, the sintering time of 38min and the sintering vacuum degree of 4 multiplied by 10 by a vacuum hot pressing sintering method-3Pa, cooling to room temperature after sintering to obtain the corrosion-resistant composite solder for the copper-aluminum transition wire clamp, wherein the shape of the obtained composite solder is any one or a mixture of powder, strips, rods and sheets.
Example 5
The corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following raw materials in percentage by weight: 22% of Al, 0.6% of Ag, 1% of Cu, 0.2% of rare earth elements, 0.12% of graphene and the balance of Zn. The graphene is a graphene nano sheet with the thickness of 15nm and the size of 10 mu m,
the preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp comprises the following steps:
(1) weighing the raw materials of the composite solder according to the weight percentage;
(2) firstly, crushing and dispersing the graphene nano sheets weighed in the step (1) by using an ultrasonic cell crusher, then fully mixing the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment, and centrifuging to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at a high temperature of 450 ℃ under the sintering pressure of 30MPa for 40min by using a vacuum hot pressing sintering methodJunction vacuum degree of 5X 10-3Pa, cooling to room temperature after sintering to obtain the corrosion-resistant composite solder for the copper-aluminum transition wire clamp, wherein the shape of the obtained composite solder is any one or a mixture of powder, strips, rods and sheets.
Comparative example 1
The corrosion-resistant composite solder for the copper-aluminum transition wire clamp is not added with graphene, and the raw material composition and the preparation method are the same as those in the embodiment 4.
The wetting properties (wetting properties on copper and aluminum sheets), tensile strength, and corrosion resistance of the composite solders according to examples 1 to 5 and comparative example 1 are shown in table 1. From the analysis of corrosion kinetics, the corrosion current density indicates the intensity of the corrosion occurring; the smaller the corrosion current density, the better the corrosion resistance.
TABLE 1 Performance parameters of composite solders of examples 1-5 and comparative example 1
The data in table 1 show that the wettability, tensile strength and corrosion current density of the brazing filler metal in the embodiments 1 to 5 of the invention are superior to those of the brazing filler metal in the comparative example 1, which indicates that the addition of graphene increases the proportion of eutectic structures of the brazing filler metal, and refines crystal grains of the brazing filler metal, so that the wettability and spreadability and tensile strength of the brazing filler metal are improved, and the graphene and metal in the brazing filler metal form a laminated structure through vacuum hot-pressing sintering, so that the entry of corrosion media such as water and oxygen is blocked, and the corrosion resistance of the composite brazing filler metal is improved; however, as can be seen from examples 1 to 5, as the addition amount of the graphene in the solder is continuously increased, the wettability, tensile strength and corrosion current density of the solder are continuously increased and then decreased, because the excessive graphene and the metal in the solder are sintered in a vacuum hot pressing manner due to the excessive amount of the graphene, sintering agglomeration is easily caused, crystal grains of the solder are increased, a laminated structure is difficult to form between the graphene and the metal, the wettability and tensile strength of the solder are reduced, and corrosion media such as water and oxygen enter through agglomerated gaps to accelerate corrosion of the wire clamp.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (8)
1. The corrosion-resistant composite solder for the copper-aluminum transition wire clamp is characterized by comprising the following raw materials in percentage by weight: 10-22% of Al, 0.3-0.6% of Ag, 0.4-1% of Cu, 0.05-0.2% of rare earth elements, 0.01-0.12% of graphene and the balance of Zn.
2. The corrosion-resistant composite solder for the copper-aluminum transition wire clamp according to claim 1, wherein the weight percentage of the graphene is 0.01-0.09%.
3. The corrosion-resistant composite solder for the copper-aluminum transition wire clamp according to claim 1 or 2, wherein the graphene is a graphene nanosheet, the graphene nanosheet is 3-15nm in thickness and 3-10 μm in size.
4. The corrosion-resistant composite solder for the copper-aluminum transition wire clamp according to any one of claims 1 to 3, wherein the graphene is prepared by reducing graphene oxide with hydrazine hydrate.
5. The corrosion-resistant composite solder for the copper-aluminum transition wire clamp according to claim 1, wherein the composite solder is any one of powder, strip, rod and sheet or a mixture of solder in several shapes.
6. A preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) weighing the raw materials of the composite solder in percentage by weight;
(2) firstly, crushing and dispersing the graphene weighed in the step (1) by using an ultrasonic cell crusher, and then fully mixing and centrifuging the metal raw material powder weighed in the step (1) and the graphene powder subjected to dispersion treatment to obtain a mixture of the metal raw material and the graphene powder;
(3) uniformly mixing the metal raw material obtained in the step (2) and the mixture of graphene powder by using a mixer;
(4) and (4) sintering the mixture of the metal raw material and the graphene powder uniformly mixed in the step (4) at a high temperature by using a vacuum hot pressing sintering method, and cooling to room temperature after sintering to obtain the corrosion-resistant composite brazing filler metal.
7. The preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp as claimed in claim 6, wherein the diameter of the metal raw material powder in the step (2) is 10-100 μm.
8. The preparation method of the corrosion-resistant composite solder for the copper-aluminum transition wire clamp as claimed in claim 6, wherein the sintering temperature of the vacuum hot-pressing sintering in the step (4) is 400-450 ℃, the sintering pressure is 30MPa, the sintering time is 30-40min, and the sintering vacuum degree is 1 x 10-3-5×10-3Pa。
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