CN110983096A - Method for preparing silver matrix oxide electric contact material by internal oxidation method capable of improving fusion welding resistance - Google Patents
Method for preparing silver matrix oxide electric contact material by internal oxidation method capable of improving fusion welding resistance Download PDFInfo
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- CN110983096A CN110983096A CN201911245914.3A CN201911245914A CN110983096A CN 110983096 A CN110983096 A CN 110983096A CN 201911245914 A CN201911245914 A CN 201911245914A CN 110983096 A CN110983096 A CN 110983096A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
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Abstract
The invention discloses a method for preparing a silver matrix oxide electric contact material by an internal oxidation method capable of improving fusion welding resistance. When the smelting temperature is raised to 1380-1500 ℃, the excessive iron and the silver are added to be fully alloyed, and the mixture is stirred for multiple times in the refining process, so that the iron element is uniformly distributed in the silver matrix, then other main metal elements are added to prepare silver alloy melt, and finally the silver alloy melt is cast into a cylindrical spindle. After the spindle is cooled, the iron which is previously fused into the silver matrix is gradually separated out along with the reduction of the solid solubility and is uniformly distributed. When the fusion welding position appears in a large number of gathering points or is overlapped with gathering connecting lines, the contact is easy to break due to the fact that iron particles are not combined with AgMeO alloy after iron surface oxides are burnt through; and the uniform distribution of iron particles greatly improves the breaking probability, and reduces the fusion welding force of the silver matrix oxide electric contact material from the side surface, thereby improving the fusion welding resistance of the material.
Description
Technical Field
The invention belongs to the field of electric contact material preparation, and particularly relates to a method for preparing a silver matrix oxide electric contact material by an internal oxidation method for improving fusion welding resistance.
Background
In the field of electrical contacts, silver matrix oxide materials have an important position in the whole electrical contact material system due to excellent comprehensive electrical properties. The metal oxide and the additive in the silver matrix belong to a reinforcing phase for the silver matrix, and the arc erosion resistance and the fusion welding resistance of the silver matrix are improved in a dispersion strengthening mode. In the process of electric contact, the welding of the contact is a common failure mode, so how to improve the welding resistance of the electric contact material is an important direction in the research field of the electric contact material.
The fusion welding of the contact refers to the phenomenon that metals in the contact area of the contact are fused and combined together, and the fusion welding is divided into static fusion welding and dynamic fusion welding according to the formation reason. Static fusion welding is a phenomenon that in a closed contact with fixed contact connection or enough contact force, a conductive spot and metal nearby the conductive spot are melted to be welded due to heating of contact resistance; the dynamic fusion welding refers to a fusion welding phenomenon which is caused by that liquid metal bridging is generated between contacts or the contacts are locally melted by heat generated by electric arc energy when the contact pressure of the contacts is changed at or above zero value in the process of connecting or disconnecting a circuit. In the practical application process, the fusion welding resistance of the contact material is improved by two main ways: one is to increase the heat-conducting property, improve the melting point and hot melt of the material; another is to reduce the welding force of the contact material.
There are three common manufacturing processes for conventional silver matrix oxide electrical contact materials: internal oxidation process, pre-oxidation process and powder metallurgy process.
Patent CN201810926087.3 discloses a process for manufacturing a silver tin oxide weighted rare earth contact material by using a powder metallurgy process to mix Ag and SnO2The rare earth material and the contact are mixed and pressed, and then the components of the material are homogenized through two times of extrusion-rolling, so that the high-temperature stability of the material is optimized finally, the contact has high electric conductivity and high thermal conductivity, and the contact has good arc erosion resistance.
Patent CN201810494269.8 discloses a silver-tin oxide electrical contact material and a preparation method thereof, wherein a powder metallurgy process is adopted to ball mill and mix silver bismuth alloy powder or silver copper alloy powder or silver bismuth copper alloy powder and tin oxide powder, and the mixture is sintered and processed into an electrical contact material, and the addition of bismuth and copper improves the capability of liquid silver wetting tin oxide under the working state of a silver tin oxide contact and improves the fusion welding resistance of the material.
Patent CN201711445714.3 discloses a method for preparing a silver-based alloy contact material, which comprises processing silver powder, tungsten powder, nickel powder, copper powder, aluminum powder, titanium carbide and other components according to a certain proportion by using a powder oxidation process, and then performing cold pressing, high-temperature sintering, repressing, extruding and drawing processes to prepare the silver-based alloy contact material.
Patent 201210297893.1 and patent ZL201310700969.5 disclose a method for improving the fusion welding resistance of materials, but both are only suitable for pre-oxidation process, and are not suitable for improving the fusion welding resistance of materials with internal oxidation process.
The conventional method for improving the fusion welding resistance of the silver matrix oxide material by the internal oxidation process is to improve the content of the oxide or add a metal additive capable of forming an alloy with silver, and the fusion welding resistance of the material can be improved only by requiring the metal oxide of the additive to have a larger wetting angle with the silver matrix, but the method can cause the reduction of the electrical conductivity of the electrical contact material and the improvement of the arc energy, so how to improve the fusion welding resistance of the internal oxidation method silver matrix oxide electrical contact material on the basis of not influencing the electrical conductivity has important practical application value.
Disclosure of Invention
In order to solve the problems and the defects of the prior art, the invention aims to provide a method for preparing a silver matrix oxide electric contact material by an internal oxidation method capable of improving the fusion welding resistance, and the fusion welding resistance of the material is improved by reducing the fusion welding force of the material without influencing the conductivity of the silver matrix oxide material.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
(1) heating and smelting silver to form silver solution;
(2) continuously raising the temperature to 1300 ℃ and 1500 ℃, adding 0.4-1.0% of iron to fully alloy with the silver, and stirring for multiple times in the refining process to uniformly distribute the iron into the silver matrix to obtain silver-iron alloy melt;
(3) reducing the temperature to 1000-1100 ℃, gradually separating out iron which is melted into the silver matrix into iron particles along with the reduction of the solid solubility, uniformly distributing the iron particles, then adding other main metal elements to prepare silver alloy melt, and finally casting the silver alloy melt into silver alloy ingots;
(4) and (3) extruding, rolling, punching and internally oxidizing the silver alloy ingot obtained in the step (3) to form a sheet contact, or extruding, drawing, internally oxidizing, pressing the ingot, extruding, drawing and making into a rivet contact, wherein in the internal oxidation process in the step (4), other main metal elements are fully oxidized into oxides, but only the surface layer of the iron particles is oxidized, and in the oxidation process, other main metal elements wrapped in the iron particles are fully paved on the surface of the iron particles due to oxidation precipitation to form a slight aggregation point or connection line aggregation similar to an oxidation crystal boundary.
The further arrangement is that the adding form of the iron in the step (2) is silver skin coated iron powder or silver iron alloy.
It is further provided that the alloy ingot cast in step (3) has a cylindrical shape.
The silver alloy is characterized in that the main metal element is one or a combination of more of copper, cadmium, tin and indium, and the mass percentage of the main metal element in the silver alloy melt is 5-15%.
The invention has the advantages that:
according to the phase diagram of the silver-iron alloy shown in fig. 1, at normal temperature, the solid solubility of iron in the silver matrix is about 0.12%, but when the melting temperature is raised to 1380-1500 ℃, the solid solubility can reach more than 1%, at this time, the excessive iron and the silver can be added to fully alloy, and the mixture is stirred for multiple times in the refining process, so that the iron element is uniformly distributed in the silver matrix, then other main metal elements (expressed by Me, the same applies below) are added to prepare silver alloy melt, and finally the silver alloy melt is cast into a cylindrical spindle.
After the spindle is cooled, the iron which is previously fused into the silver matrix is gradually separated out along with the reduction of the solid solubility and is uniformly distributed. In the subsequent internal oxidation process, Me is fully oxidized into MeO, but only the surface layer of the iron particles is oxidized, and Me wrapped in the iron particles can be fully paved on the surface of the iron particles due to oxidation precipitation in the oxidation process to form a slight aggregation point or connection line aggregation similar to an oxidation grain boundary. Thus, under the microscopic condition, when the fusion welding position appears at a large number of aggregation points or is superposed with aggregation connecting lines, the iron particles are easy to break because of the non-combination of the iron particles and the AgMeO alloy after burning through the oxide on the surface of the iron; and the uniform distribution of iron particles greatly improves the breaking probability, and reduces the fusion welding force of the silver matrix oxide electric contact material from the side surface, thereby improving the fusion welding resistance of the material.
The metallographic structure of the product manufactured by the method is shown in figure 2, and obvious iron particles are separated out from the matrix.
Compared with the traditional process, the invention has the advantages and positive effects that:
1. the invention provides a simple and effective method for improving the conductivity of the internal oxidation method silver matrix oxide without reducing the conductivity; the tensile strength of the material is reduced, and the fusion welding force of the material is reduced, so that the fusion welding resistance of the internal oxidation method silver matrix oxide material is improved.
2. The invention only adds iron element and changes the feeding sequence of each element on the original production mode, other production processes are not changed, and the feasibility of mass production is realized.
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 introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 phase diagram of silver-iron alloy;
FIG. 2 is a metallographic structure of a silver matrix with iron particles precipitated in the process of the invention, wherein FIG. 2a is a 200-fold magnified perspective and FIG. 2b is a 1000-fold magnified perspective.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
The first embodiment is as follows:
a) melting 18.62kg of silver plate in an air smelting furnace to form silver melt;
b) the temperature of the silver solution is increased to 1400 ℃, and 0.08kg of iron powder wrapped by 0.3kg of silver skin is added;
c) stirring for multiple times to form homogenized alloy melt;
d) reducing the temperature of the silver alloy melt to 1100 ℃, adding 1.0kg of copper bar, and fully stirring to form silver matrix alloy;
e) casting the AgCu5 alloy into a cylindrical spindle, wherein the mass percent of iron element in the alloy spindle is 0.4%;
f) the contact is processed into the sheet contact of AgCuO (6) by an internal oxidation method through the working procedures of extrusion, hot rolling, cold rolling, punching, internal oxidation and the like.
Example two:
a) melting 17.56kg of silver plate in an air smelting furnace to form silver melt;
b) the temperature of the silver solution is increased to 1300 ℃, and 1.4kg of AgFe10 alloy wrapped by 0.3kg of silver skin is added;
c) stirring for multiple times to form homogenized alloy melt;
d) reducing the temperature of the silver alloy melt to 1000 ℃, adding 2.0kg of cadmium ingot, and fully stirring to form silver matrix alloy;
e) casting the AgCd10 alloy into a cylindrical spindle, wherein the mass percent of the iron element in the alloy spindle is 0.7%;
f) the AgCdO (11) wire rod by the internal oxidation method is processed by the working procedures of extrusion, drawing, internal oxidation, secondary extrusion and the like.
Example three:
a) melting 12.54kg of silver plate in an air smelting furnace to form silver solution;
a) the temperature of the silver melt is increased to 1400 ℃, and 4kg of AgFe5 alloy wrapped by 0.3kg of silver skin is added;
b) stirring for multiple times to form homogenized alloy melt;
c) reducing the temperature of the silver alloy melt to 1100 ℃, adding 3.0kg of tin ingot and 0.16kg of indium ingot, and fully stirring to form silver matrix alloy;
d) the AgSn15In0.8 alloy is cast into a cylindrical spindle, and the mass percent of the iron element in the alloy spindle is 1.0 percent;
e) the contact is processed into the sheet contact of AgSnO (18) In2O3(0.9) by an internal oxidation method through the working procedures of extrusion, hot rolling, cold rolling, punching, internal oxidation and the like.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (4)
1. A method for preparing a silver matrix oxide electric contact material by an internal oxidation method capable of improving fusion welding resistance is characterized by comprising the following steps:
(2) heating and smelting silver to form silver solution;
(3) continuously raising the temperature to 1300 ℃ and 1500 ℃, adding 0.4-1.0 percent of iron to fully alloy with the silver, and stirring for multiple times in the refining process to ensure that the iron is uniformly distributed in the silver matrix to obtain silver-iron alloy melt;
(3) reducing the temperature to 1000-1100 ℃, gradually separating out iron which is melted into the silver matrix into iron particles along with the reduction of the solid solubility and uniformly distributing the iron particles, then adding other low-melting-point reinforcing phase metal elements to prepare silver alloy melt, and finally casting the silver alloy melt into silver alloy ingots;
(4) and (3) extruding, rolling, punching and internally oxidizing the silver alloy ingot obtained in the step (3) to form a sheet contact, or extruding, drawing, internally oxidizing, pressing the ingot, extruding, drawing and making into a rivet contact, wherein in the internal oxidation process in the step (4), other reinforcing phase metal elements are fully oxidized into oxides, but only the surface layer of iron particles is oxidized, and other main metal elements wrapped in the iron particles are fully paved on the surface of the iron particles due to oxidation precipitation in the oxidation process to form slight aggregation points or connection line aggregation similar to oxidation crystal boundaries.
2. The method of claim 1, wherein: the addition form of the iron in the step (2) is iron powder or silver-iron alloy wrapped by silver skin.
3. The method of claim 1, wherein: the method is characterized in that: and (4) casting the alloy ingot formed in the step (3) to form a cylindrical shape.
4. The method of claim 1, wherein: the main metal element is one or the combination of a plurality of copper, cadmium, tin and indium, and the mass percentage of the main metal element in the silver alloy melt is 5-15%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911245914.3A CN110983096A (en) | 2019-12-07 | 2019-12-07 | Method for preparing silver matrix oxide electric contact material by internal oxidation method capable of improving fusion welding resistance |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911245914.3A CN110983096A (en) | 2019-12-07 | 2019-12-07 | Method for preparing silver matrix oxide electric contact material by internal oxidation method capable of improving fusion welding resistance |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053509A (en) * | 1990-01-19 | 1991-07-31 | 中外电气工业株式会社 | The inner oxidation method of contact material and the material of producing by this method |
| CN1054505A (en) * | 1990-02-28 | 1991-09-11 | 中外电气工业株式会社 | Silver-tin contact material and manufacture method thereof |
| KR20070036983A (en) * | 2005-09-30 | 2007-04-04 | 한국생산기술연구원 | Fe added silver and silver alloys and their manufacturing method thereof |
| CN101136287A (en) * | 2007-08-29 | 2008-03-05 | 桂林电器科学研究所 | High temperature resistant silver oxide contact tip material manufacturing method |
| CN105359241A (en) * | 2013-06-24 | 2016-02-24 | 三菱电机株式会社 | Electrical contact material and method for manufacturing same |
-
2019
- 2019-12-07 CN CN201911245914.3A patent/CN110983096A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053509A (en) * | 1990-01-19 | 1991-07-31 | 中外电气工业株式会社 | The inner oxidation method of contact material and the material of producing by this method |
| CN1054505A (en) * | 1990-02-28 | 1991-09-11 | 中外电气工业株式会社 | Silver-tin contact material and manufacture method thereof |
| KR20070036983A (en) * | 2005-09-30 | 2007-04-04 | 한국생산기술연구원 | Fe added silver and silver alloys and their manufacturing method thereof |
| CN101136287A (en) * | 2007-08-29 | 2008-03-05 | 桂林电器科学研究所 | High temperature resistant silver oxide contact tip material manufacturing method |
| CN105359241A (en) * | 2013-06-24 | 2016-02-24 | 三菱电机株式会社 | Electrical contact material and method for manufacturing same |
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