CN111883400B - Silver-copper composite wire for fuse and preparation method thereof - Google Patents
Silver-copper composite wire for fuse and preparation method thereof Download PDFInfo
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- CN111883400B CN111883400B CN202010865131.1A CN202010865131A CN111883400B CN 111883400 B CN111883400 B CN 111883400B CN 202010865131 A CN202010865131 A CN 202010865131A CN 111883400 B CN111883400 B CN 111883400B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
- H01H85/02—Details
- H01H85/04—Fuses, i.e. expendable parts of the protective device, e.g. cartridges
- H01H85/05—Component parts thereof
- H01H85/055—Fusible members
- H01H85/08—Fusible members characterised by the shape or form of the fusible member
- H01H85/11—Fusible members characterised by the shape or form of the fusible member with applied local area of a metal which, on melting, forms a eutectic with the main material of the fusible member, i.e. M-effect devices
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Abstract
The invention provides a silver-copper composite wire for a fuse and a preparation method thereof, wherein the silver-copper composite wire is composed of a copper core and a pure silver layer arranged on the outer side of the copper core, the thickness of the pure silver layer is 0.01-0.1 mm, and the silver-copper layer generates a silver-copper alloy through a solid-phase diffusion reaction. The outer layer of pure silver material has good conductivity, and bears the conductive function of the circuit, and the core copper material saves the use amount of pure silver and reduces the cost. The silver-copper composite wire provided by the invention has a low melting point, when a melt is fused, the low melting point silver-copper alloy is firstly fused, and by utilizing the metallurgical effect, the fused silver-copper alloy can timely spread and fuse copper and silver on two sides, so that the melt is rapidly fused, and a circuit is protected in time.
Description
Technical Field
The invention relates to the technical field of electrical materials, in particular to a silver-copper composite wire for a fuse and a preparation method thereof.
Background
Pure silver has excellent electric and heat conductivity, is an ideal melt material, and easily meets the requirement of high breaking current capability. However, the cost of pure Ag is high, which significantly increases the manufacturing cost of the fuse, and from the perspective of saving resources, the fuse is a loss product, and is discarded after failure, which causes a great deal of waste of silver resources, and is not favorable for industry development.
As a substitute for pure silver, a silver-substitute melt material is a research hotspot in the field of melt materials at present, wherein chemical copper silver plating materials are a class of products which are applied more at present, but the melt material still has a plurality of problems found in use: (1) the existing copper silver-plating products mostly adopt electrochemical silver plating, and the electrolyte contains highly toxic cyanide, so that the concept of green development is not satisfied; (2) the coating of the existing silver-plated product is influenced by multiple factors, and the thickness of the coating is unstable, so that the resistivity of the subsequent product is unstable.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a silver-copper composite wire for a fuse, which comprises a copper core and a silver layer arranged on the outer side of the copper core, wherein the thickness of the silver layer is 0.01-0.1 mm, the conductivity of a pure silver material on the outer layer is good, the silver-copper composite wire can play a circuit conductive function, the consumption of pure silver in a copper material on a core part is reduced, and the cost is reduced. The silver-copper composite wire provided by the invention has a low melting point, when a melt is fused, the low melting point silver-copper alloy is firstly fused, and by utilizing the metallurgical effect, the fused silver-copper alloy can timely spread and fuse copper and silver on two sides, so that the melt is rapidly fused, and a circuit is protected in time.
The second purpose of the invention is to provide a preparation method of the silver-copper composite wire for the fuse, which has the advantages of good processing performance, uniform distribution of the silver layer on the outer layer, convenience for subsequent production, environmental protection and harmlessness compared with the traditional silver-plated wire, and avoids environmental pollution and electroplating solution pollution generated in the electroplating process.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the silver-copper composite wire for the fuse comprises a copper core and a pure silver layer arranged on the outer side of the copper core, wherein the thickness of the pure silver layer is 0.01-0.1 mm, preferably 0.01-0.08 mm, and more preferably 0.01-0.06 mm.
Preferably, the purity of the pure silver layer is more than or equal to 99.99%, the copper core is oxygen-free copper, and the purity of the oxygen-free copper is more than or equal to 99.95%.
The preparation method of the silver-copper composite wire for the fuse comprises the following steps:
(a) respectively smelting silver and copper, and respectively pouring the smelted silver and copper into a mould to prepare a silver ingot and a copper ingot;
(b) extruding and drawing the silver ingot obtained in the step (a) into silver wires with the diameter of 0.1-1 mm;
(c) removing shrinkage cavities and impurities on the surface of the copper ingot obtained in the step (a), winding the silver wire dense layer obtained in the step (b) to the periphery of the copper ingot to obtain a silver-copper composite ingot with a double-layer structure, and carrying out solid-phase diffusion reaction;
(d) and (c) drawing the silver-copper composite ingot subjected to the solid phase diffusion reaction in the step (c) into a silver-copper composite wire.
Preferably, in step (a), the smelting is carried out in a vacuum smelting furnace.
Preferably, in step (a), the material of the mold used for the smelting and the casting is highly dense graphite, and more preferably, the mold is subjected to vacuum deoxidation heat treatment before use.
Preferably, in the step (b), before the extruding step, the silver ingot is thermally insulated to 700-750 ℃.
Preferably, in step (c), the solid phase diffusion reaction is carried out in a vacuum diffusion furnace.
Preferably, in the step (d), the temperature of the vacuum diffusion is 700-780 ℃ and the time is 3-5 h.
Preferably, in the step (d), the step of drawing the silver-copper composite wire specifically includes:
and (c) performing mechanical external circle finish machining on the silver-copper composite ingot subjected to the solid phase diffusion reaction in the step (c), extruding the obtained composite ingot into a silver-copper composite wire blank with the diameter of 3-10 mm, and performing multi-pass reducing drawing to obtain a filamentous silver-copper composite wire with the diameter of 0.2-1 mm.
Preferably, the extrusion is carried out using a 1000 ton horizontal extruder.
Compared with the prior art, the invention has the beneficial effects that:
(1) the silver-copper composite wire provided by the invention is composed of double-layer materials, and comprises a copper core and a silver layer arranged on the outer side of the copper core, wherein the thickness of the silver layer is 0.01-0.1 mm, the conductivity of the pure silver material on the outer layer is good, the silver layer bears the circuit conductivity function, the pure silver consumption is saved due to the copper material on the core part, and the cost is reduced.
(2) The silver-copper composite wire provided by the invention has a low melting point, the low melting point silver-copper alloy is firstly melted when the melt is fused, and the melted silver-copper alloy is spread and fused on the copper and the silver on the two sides in time by utilizing the metallurgical effect, so that the melt is rapidly fused, and the circuit is protected in time.
(3) The preparation method of the silver-copper composite wire provided by the invention has the advantages of good processing performance, uniform distribution of the outer silver layer, convenience for subsequent narrow neck processing and punching, environmental protection compared with the traditional silver-plated wire, and avoidance of environmental pollution and pollution of electroplating solution generated in the electroplating process.
(4) According to the preparation method of the silver-copper composite wire, provided by the invention, the silver and copper raw materials are respectively subjected to vacuum smelting, so that the gas content in the raw materials can be reduced, the purity of the raw materials is improved, and the resistance of the product is reduced.
(5) According to the preparation method of the silver-copper composite wire, when the melt is overloaded in the using process, the low-melting-point silver-copper alloy is firstly melted to wrap the copper and the silver matrix, and the copper and the silver are mutually permeated to form the silver-copper alloy with the melting point lower than that of the copper, so that the copper melt can be fused at a lower temperature to realize overload protection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a silver-copper composite wire for a fuse according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The silver-copper composite wire for the fuse comprises a copper core and a pure silver layer arranged on the outer side of the copper core, wherein the thickness of the pure silver layer is 0.01-0.1 mm (such as 0.05, 0.08, 0.1, 0.2, 0.5, 0.8, 0.9 and 1mm), preferably 0.01-0.08 mm, and more preferably 0.01-0.06 mm.
The silver-copper composite wire provided by the invention is composed of double-layer materials, and comprises a copper core and a silver layer arranged on the outer side of the copper core, wherein the thickness of the silver layer is 0.01-0.1 mm, the conductivity of the pure silver material on the outer layer is good, the circuit conductivity function is born, the pure silver consumption is saved by the copper material on the core part, and the cost is reduced; secondly, the silver-copper composite wire has low melting point, when the melt is fused, the low-melting-point silver-copper alloy is firstly fused, and the fused silver-copper alloy spreads and fuses copper and silver on two sides in time by utilizing the metallurgical effect, so that the melt is rapidly fused, and a circuit is protected in time; and the processing performance is good, the silver layer on the outer layer is uniformly distributed, and the subsequent narrow neck processing and punching are facilitated.
In some preferred embodiments of the present invention, the purity of the pure silver is 99.99% or more, the copper core is oxygen-free copper, and the purity of the oxygen-free copper is 99.95% or more.
The invention provides a preparation method of a silver-copper composite wire for a fuse, which comprises the following steps:
(a) respectively smelting silver and copper, and respectively pouring the smelted silver and copper into a mould to prepare a silver ingot and a copper ingot;
(b) extruding and drawing the silver ingot obtained in the step (a) into silver wires with the diameter of 0.1-1 mm (such as 1, 1.5, 2, 2.5 and 3 mm);
(c) removing shrinkage cavities and impurities on the surface of the copper ingot obtained in the step (a), winding the silver wire dense layer obtained in the step (b) to the periphery of the copper ingot to obtain a silver-copper composite ingot with a double-layer structure, and carrying out solid-phase diffusion reaction;
(d) and (c) drawing the silver-copper composite ingot obtained in the step (c) into a silver-copper composite wire.
According to the method provided by the invention, the silver and copper raw materials are respectively subjected to vacuum smelting, so that the gas content in the raw materials can be reduced, the purity of the raw materials is improved, and the product resistance is reduced; after the fine silver wire densely arranged layer is wound on the periphery of the copper bar (densely arranged layer winding means that one silver wire is wound on a copper ingot without gaps in the middle), the silver wire is placed in a vacuum diffusion furnace for sufficient diffusion, so that silver and copper atoms are mutually diffused to form metallurgical connection, and the bonding interface is firm; the composite wire with stable size and higher bonding strength can be obtained by performing small transformation ratio multi-pass processing by using a drawing processing means; compared with the traditional silver-plated wire, the processing method has the advantages of environmental protection and harmlessness, and avoids environmental pollution and electroplating solution pollution generated in the electroplating process; when the melt is overloaded in the using process, the low-melting-point silver-copper alloy is firstly melted to wrap the copper and the silver matrix, and the copper and the silver are mutually permeated to form the silver-copper alloy with the melting point lower than that of the copper, so that the copper melt can be fused at lower temperature to realize overload protection.
In some preferred embodiments of the invention, in step (a), the smelting is carried out in a vacuum smelting furnace.
In some preferred embodiments of the present invention, in step (a), the material of the mold used for the smelting and the casting is highly dense graphite, and preferably, the mold is subjected to vacuum deoxidation heat treatment before use.
In some preferred embodiments of the present invention, in the step (b), the silver ingot is heat-insulated to 700 to 750 ℃ before the extruding step.
In some preferred embodiments of the present invention, in step (c), the solid phase diffusion reaction is performed in a vacuum diffusion furnace.
In some preferred embodiments of the present invention, in step (d), the temperature of the vacuum diffusion is 700 to 780 (e.g., 700, 750, 780) DEG C, and the time is 3 to 5h (e.g., 3, 4, 5 h).
In some preferred embodiments of the present invention, in step (d), the step of drawing into the silver-copper composite wire specifically includes:
extruding the silver-copper composite ingot after the solid phase diffusion reaction in the step (c) into silver-copper composite wires with the diameter of 3-10 mm (such as 3, 4, 5, 6, 7, 8, 9 and 10mm), and drawing into filiform silver-copper composite wires with the diameter of 0.2-1 mm (0.2, 0.4, 0.6, 0.8 and 1 mm).
In some preferred embodiments of the invention, the extrusion is performed using a 1000 ton horizontal extruder.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The preparation method of the silver-copper composite wire provided by the embodiment specifically comprises the following steps:
(1) weighing pure silver with the purity of 99.99 percent and oxygen-free copper with the purity of 99.95 percent, respectively putting the pure silver and the oxygen-free copper into a crucible, putting the crucible into a vacuum smelting furnace for vacuum smelting, and respectively pouring the crucible into a mold to obtain round silver ingots and round copper ingots;
wherein the crucible for vacuum smelting and the mould for casting are made of high-purity, high-strength, high-density and high-density graphite, and the crucible and the mould are subjected to vacuum deoxidation heat treatment before use;
(2) extruding and drawing the round silver ingot into silver wires with the diameter of 1 mm;
(3) cleaning the peripheral shrinkage cavity and impurities of the round copper ingot by using a lathe;
(4) winding the fine silver wire dense layer to the periphery of the copper ingot;
(5) winding the layer into a formed double-layer structure silver-copper composite ingot, and putting the ingot into a vacuum diffusion furnace for solid phase diffusion reaction; the diffusion temperature in the vacuum diffusion furnace is 750 ℃, and the time is 3 hours;
(6) and extruding the silver-copper composite ingot with the double-layer structure formed by reaction diffusion into a silver-copper composite wire with the diameter of 3mm by a 1000-ton horizontal extruder, preserving the temperature to be above the recrystallization temperature of the silver and the copper in advance during extrusion, then carrying out hot extrusion on the silver-copper composite ingot, and drawing the silver-copper composite wire into a wire with the diameter of 0.2mm by a drawing die.
Example 2
The preparation method of the silver-copper composite wire provided by the embodiment specifically comprises the following steps:
(1) weighing pure silver with the purity of 99.99 percent and oxygen-free copper with the purity of 99.95 percent, respectively putting the pure silver and the oxygen-free copper into a crucible, putting the crucible into a vacuum smelting furnace for vacuum smelting, and respectively pouring the crucible into a mold to obtain round silver ingots and round copper ingots;
wherein the crucible for vacuum smelting and the mould for casting are made of high-purity, high-strength, high-density and high-density graphite, and the crucible and the mould are subjected to vacuum deoxidation heat treatment before use;
(2) extruding and drawing the round silver ingot into silver wires with the diameter of 3 mm;
(3) cleaning the peripheral shrinkage cavity and impurities of the round copper ingot by using a lathe;
(4) winding the fine silver wire dense layer to the periphery of the copper ingot;
(5) winding the layer into a formed double-layer structure silver-copper composite ingot, and putting the ingot into a vacuum diffusion furnace for solid phase diffusion reaction; the diffusion temperature in the vacuum diffusion furnace is 700 ℃, and the time is 5 hours;
(6) and extruding the silver-copper composite ingot with the double-layer structure formed by reaction diffusion into a silver-copper composite wire with the diameter of 10mm by a 1000-ton horizontal extruder, preserving the temperature to be above the recrystallization temperature of the silver and the copper in advance during extrusion, then carrying out hot extrusion on the silver-copper composite ingot, and drawing the silver-copper composite wire into a wire with the diameter of 1mm by a drawing die.
Example 3
The preparation method of the silver-copper composite wire provided by the embodiment specifically comprises the following steps:
(1) weighing pure silver with the purity of 99.99 percent and oxygen-free copper with the purity of 99.95 percent, respectively putting the pure silver and the oxygen-free copper into a crucible, putting the crucible into a vacuum smelting furnace for vacuum smelting, and respectively pouring the crucible into a mold to obtain round silver ingots and round copper ingots;
wherein the crucible for vacuum smelting and the mould for casting are made of high-purity, high-strength, high-density and high-density graphite, and the crucible and the mould are subjected to vacuum deoxidation heat treatment before use;
(2) extruding and drawing the round silver ingot into silver wires with the diameter of 2 mm;
(3) cleaning the peripheral shrinkage cavity and impurities of the round copper ingot by using a lathe;
(4) winding the fine silver wire dense layer to the periphery of the copper ingot;
(5) winding the layer into a formed double-layer structure silver-copper composite ingot, and putting the ingot into a vacuum diffusion furnace for solid phase diffusion reaction; the diffusion temperature in the vacuum diffusion furnace is 780 ℃ for 4 hours;
(6) and extruding the silver-copper composite ingot with the double-layer structure formed by reaction diffusion into a silver-copper composite wire with the diameter of 8mm by a 1000-ton horizontal extruder, preserving the temperature to be above the recrystallization temperature of the silver and the copper in advance during extrusion, then carrying out hot extrusion on the silver-copper composite ingot, and drawing the silver-copper composite wire into a wire with the diameter of 0.5mm by a drawing die.
Example 4
The preparation method of the silver-copper composite wire provided by the embodiment specifically comprises the following steps:
(1) weighing pure silver with the purity of 99.99 percent and oxygen-free copper with the purity of 99.95 percent, respectively putting the pure silver and the oxygen-free copper into a crucible, putting the crucible into a vacuum smelting furnace for vacuum smelting, and respectively pouring the crucible into a mold to obtain round silver ingots and round copper ingots;
wherein the crucible for vacuum smelting and the mould for casting are made of high-purity, high-strength, high-density and high-density graphite, and the crucible and the mould are subjected to vacuum deoxidation heat treatment before use;
(2) extruding and drawing the round silver ingot into silver wires with the diameter of 3 mm;
(3) cleaning the peripheral shrinkage cavity and impurities of the round copper ingot by using a lathe;
(4) winding the fine silver wire dense layer to the periphery of the copper ingot;
(5) winding the layer into a formed double-layer structure silver-copper composite ingot, and putting the ingot into a vacuum diffusion furnace for solid phase diffusion reaction; the diffusion temperature in the vacuum diffusion furnace is 750 ℃, and the time is 5 hours;
(6) and extruding the silver-copper composite ingot with the double-layer structure formed by reaction diffusion into a silver-copper composite wire with the diameter of 8mm by a 1000-ton horizontal extruder, preserving the temperature to be above the recrystallization temperature of the silver and the copper in advance during extrusion, then carrying out hot extrusion on the silver-copper composite ingot, and drawing the silver-copper composite wire into a wire with the diameter of 0.8mm by a drawing die.
Examples of the experiments
In 20 ℃ experimental environment, resistance measurement is carried out on a traditional silver-plated wire (comparative example) with the diameter of 0.8mm and a product sample prepared in embodiment 4 by adopting QJ84 type digital direct current bridge measurement, in order to eliminate the influence of contact potential, a current commutation method is adopted, a forward reading and a reverse reading are taken, and the arithmetic mean value of two resistance measurement values is taken.
Finally, the resistivity is calculated by using a resistivity calculation formula (formula: rho ═ R)Tπr2/T0Where ρ is the resistivity, RTIs the resistance value at T temperature, r is the wire diameter, T0Is the temperature coefficient). Specific resistivity values are shown in table 1 below.
Table 1 resistivity test results
From the experimental results, the resistivity of the silver-copper composite wire provided by the present application was reduced by about 6% as compared with the silver-plated wire provided by the comparative example.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (12)
1. The preparation method of the silver-copper composite wire for the fuse is characterized in that the silver-copper composite wire is composed of a copper core and a pure silver layer arranged on the outer side of the copper core, and the thickness of the pure silver layer is 0.01-0.1 mm;
the preparation method of the silver-copper composite wire for the fuse comprises the following steps:
(a) respectively smelting silver and copper, and respectively pouring the smelted silver and copper into a mould to prepare a silver ingot and a copper ingot;
(b) extruding and drawing the silver ingot obtained in the step (a) into silver wires with the diameter of 0.1-1 mm;
(c) removing shrinkage cavities and impurities on the surface of the copper ingot obtained in the step (a), winding the silver wire dense layer obtained in the step (b) to the periphery of the copper ingot to obtain a silver-copper composite ingot with a double-layer structure, and carrying out solid-phase diffusion reaction;
(d) and (c) drawing the silver-copper composite ingot subjected to the solid phase diffusion reaction in the step (c) into a silver-copper composite wire.
2. The method of claim 1, wherein the pure silver layer has a thickness of 0.01 to 0.08 mm.
3. The method of claim 1, wherein the pure silver layer has a thickness of 0.01 to 0.06 mm.
4. The method of claim 1, wherein the purity of the pure silver layer is greater than or equal to 99.99%, the copper core is oxygen-free copper, and the purity of the oxygen-free copper is greater than or equal to 99.95%.
5. The method of manufacturing a silver-copper composite wire for a fuse according to claim 1, wherein in step (a), the melting is performed in a vacuum melting furnace.
6. The method of manufacturing a silver-copper composite wire for a fuse according to claim 1, wherein in step (a), the material of the mold used for the melting and the pouring is graphite.
7. The method of manufacturing a silver-copper composite wire for a fuse according to claim 1, wherein in step (a), a vacuum deoxidation heat treatment is performed before the use of the mold.
8. The method of claim 1, wherein the silver ingot is heat-insulated to 700 to 750 ℃ before the extruding step in the step (b).
9. The method of manufacturing a silver-copper composite wire for a fuse according to claim 1, wherein in the step (c), the solid phase diffusion reaction is performed in a vacuum diffusion furnace.
10. The method for preparing a silver-copper composite wire for a fuse according to claim 9, wherein the temperature of the vacuum diffusion is 700 to 780 ℃ for 3 to 5 hours.
11. The method for preparing a silver-copper composite wire for a fuse according to claim 1, wherein in the step (d), the step of drawing the silver-copper composite wire specifically comprises:
and (c) performing mechanical external circle finish machining on the silver-copper composite ingot subjected to the solid phase diffusion reaction in the step (c), extruding the obtained composite ingot into a silver-copper composite wire blank with the diameter of 3-10 mm, and performing multi-pass reducing drawing to obtain a filamentous silver-copper composite wire with the diameter of 0.2-1 mm.
12. The method of manufacturing a silver-copper composite wire for a fuse according to claim 11, wherein the extrusion is performed using a 1000-ton horizontal extruder.
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| JPH0547294A (en) * | 1990-10-18 | 1993-02-26 | Sumitomo Electric Ind Ltd | Conductor for fuse |
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| CN107303609A (en) * | 2016-04-18 | 2017-10-31 | 华东师范大学 | A kind of nanometer-level silver copper-clad recombination line and its preparation method and application |
| CN109585235A (en) * | 2018-12-14 | 2019-04-05 | 郑州机械研究所有限公司 | A kind of sandwich structure silver-bearing copper melt |
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