CN107591257B - Silver-based multilayer composite electric contact material and preparation method thereof - Google Patents
Silver-based multilayer composite electric contact material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silver-based multilayer composite electric contact material and a preparation method thereof, and the silver-based multilayer composite electric contact material comprises a working layer, an intermediate layer, a welding layer and a brazing filler metal layer, wherein the intermediate layer is positioned between the working layer and the welding layer, a pure silver or silver alloy brazing filler metal layer is arranged between the intermediate layer and the working layer, the welding layer is made of cheap metal iron or iron-based alloy, the intermediate layer is made of cheap metal copper or copper alloy, and the working layer is made of one of AgMeO systems. The material is prepared by adopting directional composite rolling, continuous diffusion annealing and cold rolling. In the invention, due to the existence of Cu and Fe, a large amount of silver can be saved, and the cost is greatly reduced; the invention has the advantages of simple and controllable operation process, good material consistency, strong implementability and the like, is suitable for large-scale production, and the prepared silver-based multilayer composite electric contact material has high electric conduction, good bonding strength and weldability, beautiful contact positioning and small influence on thermal deformation of welding pieces, and can be widely applied to the industry of temperature controllers.
Description
Technical Field
The invention discloses a silver-based multilayer composite electric contact material and a preparation method thereof, in particular relates to a multilayer metal composite electric contact material, and belongs to the technical field of electric contact materials of low-voltage electric appliances.
Background
The silver-based metal oxide (AgMeO) contact material is a material with dispersed metal oxide particles distributed in a silver matrix, has excellent conductivity, fusion welding resistance, arc erosion resistance and service life, and has wide application prospect in low-voltage appliances.
AgMeO, AgM copper clad bimetal composite rivets and AgM copper clad and alloy thereof bimetal composite strip electric contact materials are widely used in low-voltage electric appliances such as low-power relays and switches. Typically, such bimetallic composite strips are less than 30% of the overall thickness and are typically produced by heavy plastic deformation-heat treatment-rolling to a finished product. The thickness of the working layer of the electric contact used in the controllers of medium-power and high-power AC/DC contactors, switches and the like is more than 30 percent of the whole thickness. Still using a large amount of AgSnO2The electric contact materials of the series, AgZnO series, AgCuO series, AgCdO series, etc. have high cost and large consumption of silver resources.
Saving silver and reducing cost are the key research contents of the current electric contact industry. Therefore, the double-layer or multi-layer electric contact material has been a hot point of research because of the small amount of noble metal, good comprehensive performance and low price. In recent years, research on compounding techniques and compounding processes has been vigorously conducted in countries such as germany, japan, and the uk. The current methods for manufacturing the multilayer electric contact material mainly comprise cold pressing compounding, diffusion welding, explosion welding, roll welding and the like. Although the above composite techniques have been applied to production and have respective advantages, there are some inevitable disadvantages that the bonding interface of the explosive welding material is liable to exhibit wave shape to affect the bonding strength, and the product size is difficult to control, and continuous production is impossible.
Through retrieval, the Chinese patent with the application number of CN200710065631.1 and the publication number of CN101034632A discloses a silver-based three-layer metal composite electric contact material, which is a three-layer material in a metallographic structure, the thickness of a working layer accounts for 32% of the whole thickness, the reduction of silver consumption and production cost is not facilitated, AgMeO (or AgM) and Cu are welded together by adopting brazing filler metal in a vacuum furnace, and then the brazing filler metal is cold-rolled to the thickness of a finished product, the flow of the preparation process is simple, but the preparation cost is relatively high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a silver-based multilayer composite electric contact material and a preparation method thereof, which can reduce the cost of silver consumption, material preparation and the like, and the material can be used for low-voltage electric appliances such as low-power relays, switches and the like.
According to a first aspect of the invention, a silver-based multilayer composite electric contact material is provided, which comprises a working layer, an intermediate layer, a welding layer and a brazing filler metal layer, wherein the intermediate layer is positioned between the working layer and the welding layer, a pure silver or silver alloy brazing filler metal layer is arranged between the intermediate layer and the working layer, the welding layer is made of cheap metal iron or iron-based alloy, the intermediate layer is made of cheap metal copper or copper alloy, and the working layer is made of one of AgMeO systems.
Preferably, the thickness of the welding layer accounts for 10-30% of the total thickness of the composite electric contact material, the thickness of the middle layer accounts for 50-70%, and the thickness of the working layer accounts for 10-30%.
Preferably, the solder layer is designed to be planar or bubble point, i.e. the surface is provided with protrusions.
The silver-based multilayer composite electric contact material is a multilayer composite AgMeO/Cu/Fe electric contact material which is in a gradient structure and formed by a working layer AgMeO, an intermediate layer Cu and a welding layer Fe.
The multilayer composite AgMeO/Cu/Fe electric contact material provided by the invention is characterized in that the AgMeO is AgSnO2One of series, such as AgZnO series, AgCuO series, and AgCdO series.
According to a second aspect of the present invention, there is provided a method for preparing a silver-based multilayer composite electrical contact material, comprising the steps of:
a. placing AgMeO strips or plates at the pure silver or silver alloy brazing filler metal, and compounding, rolling and thermally treating the AgMeO and the pure silver or silver alloy brazing filler metal layer through rolling to obtain a working layer AgMeO material;
b. placing the middle layer between the working layer AgMeO and the welding layer, and compounding the materials by rolling to form a multi-layer composite electric contact material;
c. carrying out heat treatment on the multilayer composite electric contact material;
d. and rolling the heat-treated material to the required thickness of the product.
And a, in the step a, the compounding is cold compounding, and the AgMeO and the pure silver interface after compounding are required to be combined compactly and have no cracking defect.
And a step a, wherein the rolling is hot rolling, and the compounded material is subjected to heat preservation for 0.5-3 h at 700-900 ℃ in the air, so that effective diffusion layers are formed on interfaces of different materials, and the bonding strength of the interfaces is enhanced.
And a step a, wherein the heat treatment is diffusion annealing at 650-800 ℃ for 1-5 h. The heat treatment can relieve residual stress at the interface.
And a step a, wherein the thickness of the pure silver or silver alloy solder layer accounts for 10-20% of the total thickness of the working layer.
And c, in the step b, the rolling is cold rolling, the rolling speed is 1-3 m/min, and the speed is low, so that the interface bonding is firm.
In the step c, the heat treatment is diffusion annealing treatment; the annealing temperature is 350-500 ℃, the annealing speed is 0.1-1 mm/min, the protective atmosphere is argon, and the argon flow is 0.2-1 m 3/h. The heat treatment can relieve residual stress at the interface.
And d, rolling in the step d is cold rolling, the rolling speed is 50-100 m/min, the rolling speed is high, the interface bonding is firm, and the speed is accelerated only by thinning the thickness.
In the above step e, the method further comprises, after step d:
step f, slitting and blanking the product to obtain a final product with the required specification;
wherein the slitting is to cut the composite material into a desired width; the blanking is to punch the material after slitting into the peripheral size of the required product.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, due to the existence of Cu and Fe, a large amount of silver can be saved, and the cost is greatly reduced.
The invention combines the market demands of AgMeO electrical contact materials and silver saving, takes cheap metal copper as a bridge connection and metal iron as a welding layer, and adopts the processes of directional composite rolling, continuous diffusion annealing, cold rolling, stripping and the like to prepare the multilayer composite AgMeO/Cu/Fe electrical contact material with a gradient structure. The composite material has the advantages of silver saving, low cost, simple and controllable operation process, good material consistency, strong implementability and the like, is suitable for large-scale mass production, and has the characteristics of high conductivity, high plasticity, good bonding strength and welding performance.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of a method in an embodiment of the invention;
FIG. 2 is a schematic diagram of the main structure of an AgMeO strip or plate in an embodiment of the invention after being compounded with a pure silver or silver alloy solder;
FIGS. 3a and 3b are gradient AgSnO in the embodiments of the present invention2A metallographic photograph of a/Cu/Fe multi-layer composite electric contact material strip and a bubble point after blanking;
FIG. 4 is a metallographic photograph of an AgCdO/Cu/Fe multi-layer composite electrical contact strip with a gradient structure in an embodiment of the invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
This example uses AgSnO2The specific preparation process of the/Cu/Fe multilayer composite electric contact material is as follows:
(1) AgSnO is obtained by powder metallurgy technology2Material, and AgSnO2Rolling the material into AgSnO with certain thickness and certain specification2A plate material;
(2) placing the AgSnO2 plate in pure stateAt the silver or silver alloy solder, performing cold compounding on AgSnO2 and a pure silver solder layer; carrying out hot rolling after heat preservation is carried out for 3h at 850 ℃ in the air, wherein the thickness of the pure silver solder layer accounts for 15% of the total thickness of the working layer; then diffusion annealing heat treatment is carried out, the annealing temperature is 650 ℃ and the annealing time is 5h, and the working layer AgSnO is obtained2A material.
(3) Placing the middle layer Cu in the working layer AgSnO2Rolling the material into a multi-layer composite electric contact material between the welding layer Fe and the welding layer by cold rolling, wherein the rolling speed is 3 m/min;
(4) carrying out diffusion annealing heat treatment on the composite material; the annealing temperature is 400 ℃, the annealing speed is 0.5m/min, the protective atmosphere is argon, and the argon flow is 0.4m3/h；
(5) Cold rolling the annealed material at the rolling speed of 50m/min to the required thickness of the product;
(6) the product is cut into strips, and the edge part is cut off to obtain the AgSnO2the/Cu/Fe multi-layer composite electric contact strip or plate; the plate or the strip is blanked to obtain products with required specifications, such as bubble points and the like.
Example 2
In the embodiment, taking an AgCdO/Cu/Fe multilayer composite electrical contact material as an example, the specific preparation process is as follows:
(1) the AgCdO material is obtained through an internal oxidation technology, and is rolled to a certain thickness, so that an AgCdO plate with a certain specification is obtained;
(2) placing the AgCdO plate at the position of the pure silver or silver alloy solder, and performing cold compounding on the AgCdO and the pure silver solder layer; carrying out hot rolling after heat preservation is carried out for 2.5h at 860 ℃ in the air, wherein the thickness of the pure silver brazing filler metal layer accounts for 18% of the total thickness of the working layer; and then carrying out diffusion annealing heat treatment, wherein the annealing temperature is 700 ℃ and the annealing time is 4h, so as to obtain the AgCdO material of the working layer.
(3) Placing the middle Cu layer between the AgCdO working layer and the Fe welding layer, and rolling the material into a multi-layer composite electric contact material by cold rolling at the rolling speed of 2.5 m/min;
(4) carrying out diffusion annealing heat treatment on the composite material; the annealing temperature is 450 ℃, the annealing speed is 0.8m/min, and the protective atmosphere is argonThe flow of gas and argon is 0.6m3/h；
(5) Cold rolling the annealed material at the rolling speed of 55m/min to the required thickness of the product;
(6) the product is stripped, and the edge part is cut off to obtain the AgCdO/Cu/Fe multilayer composite electric contact strip or plate; the plate or the strip is blanked to obtain products with required specifications, such as bubble points and the like.
Example 3
In the embodiment, taking AgCuO/Cu/Fe multilayer composite electrical contact material as an example, the specific preparation process is as follows:
(1) the AgCuO material is obtained through smelting atomization and internal oxidation technologies, and is rolled to a certain thickness to obtain an AgCuO plate with a certain specification;
(2) placing the AgCuO plate at the position of pure silver or silver alloy solder, and performing cold compounding on the AgCuO and the pure silver solder layer; carrying out hot rolling after heat preservation for 3h at 800 ℃ in the air, wherein the thickness of the pure silver solder layer accounts for 20% of the total thickness of the working layer; and then carrying out diffusion annealing heat treatment, wherein the annealing temperature is 720 ℃ and the annealing time is 3h, so as to obtain the AgCuO material of the working layer.
(3) Placing the middle layer Cu between the working layer AgCuO and the welding layer Fe, and rolling the material into a multi-layer composite electric contact material by cold rolling at the rolling speed of 3 m/min;
(4) carrying out diffusion annealing heat treatment on the composite material; the annealing temperature is 430 ℃, the annealing speed is 1.1m/min, the protective atmosphere is argon, and the argon flow is 0.5m3/h；
(5) Cold rolling the annealed material at the rolling speed of 58m/min to the required thickness of the product;
(6) the product is divided into strips, and the edge part is cut off to obtain the AgCuO/Cu/Fe multi-layer composite electric contact strip or plate; the plate or the strip is blanked to obtain products with required specifications, such as bubble points and the like.
Referring to fig. 2, the schematic diagram is a main structure diagram of an AgMeO strip or plate and a pure silver or silver alloy solder compounded in the embodiment of the present invention, where 1 is a U-shaped pure silver or silver alloy solder, and 2 is an AgMeO strip or plate; in the embodiment, the U-shaped brazing filler metal is adopted, the AgMeO side surface can be wrapped, the cracking tendency of the AgMeO and the silver brazing filler metal during compounding is greatly reduced, and the bonding strength of the AgMeO and the silver brazing filler metal is enhanced; the enhancement of the bonding strength is beneficial to further reducing the cracking tendency of the working layer (after AgMeO and silver solder are compounded) when the working layer, the middle layer and the welding layer are rolled and compounded, and the bonding strength of the multilayer composite material is enhanced.
Referring to fig. 3-4, according to the above embodiment, the material of the present invention includes a solder layer (Fe or Fe alloy, functioning as solder), an intermediate layer (Cu or Cu alloy, functioning as a connecting solder layer and a working layer), and a working layer (AgMeO system, which is an electric contact material working portion); from the structural point of view, the material can be divided into four layers, and as shown in the attached drawing, a thin layer of pure Ag or Ag alloy solder exists between the working layer AgMeO and the middle layer Cu.
In the material obtained by the embodiment of the invention, the thickness of the working layer AgMeO accounts for 17-22% of the whole thickness, the sum of the thicknesses of the rest layers (the middle layer, the welding layer and the brazing filler metal layer) accounts for 78-83% of the whole thickness, the thickness of the working layer accounts for a lower ratio, and a large amount of silver can be saved and the production cost can be reduced in batch production; furthermore, the thickness range of the finished product is 1.55 mm-7.5 mm, and the finished product is thicker than the existing material, so that the silver consumption can be saved.
In the material obtained by the above embodiment of the present invention, the welding layer Fe can be designed not only as a plane type, but also as a bubble point (e.g. the convex portion of the Fe layer in fig. 3 b) type. The bubble point is beneficial to achieving a better welding effect under the same welding parameters, and has good weldability, attractive positioning and small heat influence on a welding part.
The embodiment of the invention adopts the preparation of compounding, heat treatment and cold rolling, thereby being further beneficial to reducing the cost.
In conclusion, the composite material has the advantages of silver saving, low cost, simple and controllable operation process, good material consistency, strong implementability and the like, is suitable for large-scale mass production, has high conductivity, good bonding strength and weldability, beautiful contact positioning and small influence on the thermal deformation of a welding piece, and can be widely applied to the industry of temperature controllers.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. The silver-based multilayer composite electric contact material is characterized by comprising a working layer, an intermediate layer, a welding layer and a brazing filler metal layer, wherein the intermediate layer is positioned between the working layer and the welding layer, a pure silver or silver alloy brazing filler metal layer is arranged between the intermediate layer and the working layer, the welding layer is made of cheap metal iron or iron-based alloy, the intermediate layer is made of cheap metal copper or copper alloy, and the working layer is made of one of AgMeO systems; the brazing filler metal layer is a U-shaped pure silver or silver alloy brazing filler metal layer, and the side face of the working layer is wrapped by the U-shaped brazing filler metal layer;
the thickness of the welding layer accounts for 10-30% of the total thickness of the composite electric contact material, the thickness of the middle layer accounts for 50-70% of the total thickness of the composite electric contact material, and the thickness of the working layer accounts for 10-30% of the total thickness of the composite electric contact material.
2. The silver-based multilayer composite electrical contact material according to claim 1, wherein the thickness of the pure silver or silver alloy solder layer accounts for 10-20% of the total thickness of the working layer.
3. The silver-based multilayer composite electrical contact material according to any one of claims 1 to 2, characterized by one or more of the following features:
-said AgMeO system comprises: AgSnO2A linear, AgZnO-based, AgCuO-based, AgCdO-based;
the welding layer is designed to be planar or bubble point, i.e. the surface is provided with protrusions;
-said composite electrical contact material having a thickness of 1.55mm to 7.5 mm;
the thickness of the working layer AgMeO accounts for 17-22% of the total thickness of the whole composite electric contact material, and the sum of the thicknesses of the intermediate layer, the welding layer and the brazing filler metal layer accounts for 78-83% of the total thickness of the silver-based multilayer composite electric contact material.
4. A method for preparing a silver-based multilayer composite electrical contact material according to any one of claims 1 to 3, comprising the steps of:
a. placing an AgMeO strip or plate at the position of a pure silver or silver alloy solder, compounding, rolling and thermally treating the AgMeO and the pure silver or silver alloy to obtain a working layer AgMeO material; the compounding is cold compounding, and after the compounding, the AgMeO and the pure silver or silver alloy interface are combined compactly without cracking defects;
b. placing the middle layer between the working layer and the welding layer, and forming a multi-layer composite electric contact material by rolling and compounding; the rolling is cold rolling;
c. carrying out heat treatment on the multilayer composite electric contact material;
d. and rolling the heat-treated material, wherein the rolling is cold rolling to the thickness required by the product.
5. The method for preparing a silver-based multilayer composite electrical contact material according to claim 4, wherein: the step a has one or more of the following characteristics:
the rolling is hot rolling, and the compounded material is kept warm for 0.5 to 3 hours at 700 to 900 ℃ in the air;
the heat treatment is diffusion annealing, wherein the temperature is 650-800 ℃, and the time is 1-5 h.
6. The method for preparing a silver-based multilayer composite electrical contact material according to claim 4, wherein: in the step b, the rolling speed is 1-3 m/min.
7. The method for preparing a silver-based multilayer composite electrical contact material according to claim 4, wherein: in the step c, the heat treatment is diffusion annealing treatment,wherein the annealing temperature is 350-500 ℃, the annealing speed is 0.5-5 m/min, the protective atmosphere is argon, and the argon flow is 0.2-1 m3/h。
8. The method for preparing a silver-based multilayer composite electrical contact material according to claim 4, wherein: in the step d, the rolling speed is 50-100 m/min.
9. The method for preparing a silver-based multilayer composite electrical contact material according to any one of claims 4 to 8, wherein: the method further comprises after step d:
step f, slitting and blanking the product to obtain a final product with the required specification;
wherein the slitting is to cut the composite material into a desired width; the blanking is to punch the material after slitting into the peripheral size of the required product.
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| CN111719096B (en) * | 2020-06-30 | 2021-10-08 | 东莞市中一合金科技有限公司 | Micro-composite processing technology for silver cadmium oxide alloy material |
| CN112223888B (en) * | 2020-10-15 | 2023-03-28 | 温州宏丰电工合金股份有限公司 | Gradient composite material and preparation method thereof |
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