CN106067391B - Laminar silver-copper-brazing three-composite electrical contact material prepared by atomization method - Google Patents
Laminar silver-copper-brazing three-composite electrical contact material prepared by atomization method Download PDFInfo
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- CN106067391B CN106067391B CN201610504087.5A CN201610504087A CN106067391B CN 106067391 B CN106067391 B CN 106067391B CN 201610504087 A CN201610504087 A CN 201610504087A CN 106067391 B CN106067391 B CN 106067391B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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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 layered silver-copper-brazing-filler-metal three-composite electrical contact material and a preparation method thereof. The three-composite electrical contact material is obtained by preparing silver alloy powder, copper alloy powder and brazing filler metal, then preparing the silver alloy powder, the copper alloy powder and the brazing filler metal into strips, and compounding the strips. Provides a silver-saving and environment-friendly electrical contact material with low material cost and excellent comprehensive electrical performance to replace the traditional copper alloy contact, silver alloy contact and silver-copper alloy contact material.
Description
Technical Field
The invention relates to an alloy material, in particular to a preparation method of a layered silver-copper-brazing-metal three-composite electrical contact material prepared by an atomization method.
Background
The core elements of relay, contactor and circuit breaker are electric contacts (points), which bear the heavy task of connecting and breaking current, and the quality of the contact elements depends on the property and scientific and effective combination of the materials of the electric contacts (points), which is an important guarantee for the safety of electric appliances.
At present, the contact materials used in the largest amount in the market are silver alloy and copper alloy. The copper alloy contact material is partially applied to a circuit breaker and a high-voltage switch, although the copper alloy contact material is low in price, the copper alloy electrical contact is poor in oxidation resistance, the time from installation to commercial use is different, the electric appliance is long in shelf life, an oxidation film can be formed on the surface of the electrical contact when in use, in addition, when the electric appliance is disconnected in use, a large amount of heat can be released, the surface is heated and oxidized to generate the oxidation film, the contact resistance is increased, the electrical conductivity and the thermal conductivity are influenced, and the temperature rise of the electric appliance is increased; the increase of the temperature rise of the switch can accelerate the failure of all components in the switch and shorten the electric service life of the switch. Therefore, a vicious circle occurs, so that the electric appliance is damaged due to overheating and a safety accident caused by contact fusion welding occurs.
The existing silver alloy contact material is widely applied to relays, contactors and circuit breakers. Of these, silver tungsten and silver tungsten carbide graphite are typical materials used in circuit breakers.
In addition, a general miniature circuit breaker uses a contact material of silver cadmium oxide or silver graphite alloy (e.g., AgC4), or the like. However, the silver content of the contact material is very high, the silver content of the silver cadmium oxide contact material is over 85 percent, and the contact material is a mainstream product in the current contact material market, and the silver consumption is quite large every year. However, the silver resource is very limited nowadays, and with the increase of the usage amount, the price of the silver is inevitably increased, so that the cost for producing the electric contact material is high, the economic benefit of an enterprise is reduced, and the social benefit is greatly reduced. And the other metal element cadmium of the product has great environmental pollution and does not accord with the development trend of environmental protection at present. Therefore, electrical equipment manufacturers are calling for more and more high quality products by replacing precious metal silver with base metal in alloy industry. Therefore, a silver-saving and environment-friendly electrical contact material which can integrate the excellent performances of the copper alloy contact and the silver alloy contact, has low material cost and excellent integrated electrical performance is required to be found to replace the traditional copper alloy contact, silver alloy contact and silver-copper alloy contact material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a silver-saving and environment-friendly electrical contact material with low material cost and excellent comprehensive electrical performance to replace the traditional copper alloy contact, silver alloy contact and silver-copper alloy contact material.
In order to achieve the purpose, the invention provides the following technical scheme:
an atomization method for preparing laminated Ag-Cu composite electric contact material,
sequentially comprises the following steps: a silver alloy layer (the silver content is 70-99.9% in mass percentage);
a copper alloy layer (copper content is 80-99.9% by mass);
solder layers (silver copper phosphorus solder, silver copper zinc solder or amorphous solder).
The preparation method comprises the following steps:
step 1: preparing silver alloy powder and copper alloy powder by adopting an atomization method, and preparing brazing filler metal by adopting a smelting method;
step 2: carrying out oxidation treatment on the silver alloy powder and the copper alloy powder to obtain silver oxide alloy powder and copper oxide alloy powder;
and step 3: adding additives into the silver alloy powder and the copper alloy powder obtained in the step 2 according to the required proportion respectively by adopting a powder mixing method, and mixing the additives with a certain proportion of grinding materials to obtain silver alloy mixed powder and copper alloy mixed powder respectively;
and 4, step 4: respectively molding and sintering the silver alloy mixed powder and the copper alloy mixed powder to obtain a silver alloy layer ingot blank and a copper alloy layer ingot blank;
and 5: re-pressing, extruding and rolling the obtained silver alloy layer ingot blank and the copper alloy layer ingot blank to obtain a silver alloy layer strip and a copper alloy layer strip;
step 6: preparing brazing filler metal into brazing filler metal layer strips;
and 7: sequentially overlapping the silver alloy layer strip, the copper alloy layer strip and the brazing filler metal strip together for thermal compounding;
and 8: and (3) preparing the strip subjected to thermal compounding into a three-layer composite contact through processes of cold rolling, punching and the like.
As a further modification of the present invention,
the silver alloy layer comprises the following components in percentage by weight:
80-99.9% of silver;
silver layer additive:
at least one of metal, metal oxide, nonmetal, and nonmetal compound: 0.04-12%,
0.05-4% of diamond micro powder,
The total amount of the rare earth elements is 0.01-5.7%;
the copper alloy layer comprises the following components in percentage by weight:
80-99.9% of copper;
copper layer addition:
at least one of metal, metal oxide, nonmetal, and nonmetal compound: 0.1 to 10.3 percent,
0.05-4% of diamond micro powder,
The total amount of the rare earth elements is 0.01-5.7%.
As a further modification of the present invention,
the silver layer additives are as follows: the material comprises at least one of diamond micro powder, graphite, boron, aluminum, silicon, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, bismuth, scandium, yttrium, lanthanum, cerium, neodymium, ytterbium, lutetium and corresponding non-metal compounds or metal oxides;
the copper layer additives are as follows: the material comprises at least one of diamond micro powder, graphite, boron, aluminum, silicon, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, bismuth, scandium, yttrium, lanthanum, cerium, neodymium, ytterbium, lutetium and corresponding non-metal compounds or metal oxides.
As a further modification of the present invention,
the metal oxide In the silver layer additive and the copper layer additive is one or more of SnO2, ZnO, CuO, Fe2O3, CdO, In2O3, Bi2O3, Al2O3, MoO3 and ZrO2, and the rare earth element In the silver layer additive and the copper layer additive is one or more of scandium, yttrium, lanthanum, cerium, neodymium, ytterbium and lutetium.
As a further modification of the present invention,
the step 1: carrying out high-temperature smelting on silver, added metal elements and rare earth elements, wherein the smelting temperature is 1030-1400 ℃, atomizing the silver alloy powder into silver alloy powder by using high-pressure water after alloying, and then drying and sieving the silver alloy powder by using a sieve of 150-250 meshes to obtain silver alloy powder;
and (2) smelting copper, the added metal elements and rare earth elements at high temperature of 1030-1400 ℃, atomizing the copper alloy powder into copper alloy powder by using high-pressure water after alloying, drying and sieving by using a sieve of 150-250 meshes to obtain the copper alloy powder.
As a further modification of the present invention,
the oxidation temperature in the step 2 is 500-700 ℃, the oxygen pressure is 1-3 Mpa, and the time is 5-15 hours.
As a further modification of the present invention,
in the step 3, the additive is at least one of diamond, metal oxide, nonmetal and nonmetal compound, the mixing mode is ball milling, the powder mixing time is 6-10 hours, and the ball material ratio is 15-25: 1.
As a further modification of the present invention,
and in the step 4, the isostatic pressing pressure of the primary blank is 150-2000 Mpa, the density is controlled to be 75-90% of the theoretical density, the primary blank is placed into a sintering furnace, then the primary blank is vacuumized and filled with inert gas for protection, the sintering temperature is 800-1000 ℃, the time is 2-5 hours, and then the primary blank is cooled to below 50 ℃ along with the furnace and taken out of the furnace.
As a further modification of the invention:
in the step 5, the extrusion temperature is 880 ℃, and the extrusion ratio is 100;
in the step 6, the compounding temperature is 800-850 ℃, and the speed is 3-5 m/min;
in the step 7, the heat-insulated annealing is carried out on the hot-compounded strip, and meanwhile, the protection is carried out by using protective gas, the temperature is 500-650 ℃, the time is 1-3 hours, and the rolling amount of each pass is less than 20% during cold rolling.
The invention has the advantages that,
1. diamond micro powder and nickel powder which account for 0.5-40% of the total amount are added into the silver alloy layer and the copper alloy layer, and one or more of metal, nonmetal, metal oxide or nonmetal compounds in graphite, boron, aluminum, silicon, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, zirconium, niobium, molybdenum, silver, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, bismuth, scandium, yttrium, lanthanum, cerium, neodymium, ytterbium and lutetium are added into the silver alloy layer and the copper alloy layer, so that the tissue structure of the material is optimized, and the fusion welding resistance and the arc burning resistance of the material are improved.
2. By adopting the three-layer composite material, the oxidation resistance of the copper alloy material is improved, the contact resistance of the material is reduced, the conductivity of the material is improved, and the temperature rise of the switching device is reduced.
3. The three-layer composite material added with the additives, which is prepared by adopting a large-deformation thermal composite process, has firm combination between the silver alloy layer and the copper alloy layer and between the copper alloy layer and the brazing filler metal layer, improves the comprehensive performance of the product due to the composite effect, and prolongs the service life of the switching electric appliance. Because the three-layer composite process is adopted, the silver-saving effect is obvious, the silver-saving amount is about 70 percent, and the cost of the electric contact material is further reduced.
4. Because the formula, the process and the like of the invention are reasonably designed, the produced electrical contact material has the characteristics of high conductivity, low contact resistance, uniform and compact structure, high bonding strength, good oxidation resistance, excellent fusion welding resistance, electric arc burning resistance and the like.
Detailed Description
The first embodiment is as follows:
step 1, atomizing to prepare powder: comprises preparing silver metal alloy powder and copper metal alloy powder.
When the silver metal alloy powder or the copper metal alloy powder is prepared, one or two or more of aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, indium, tin, antimony, tellurium and bismuth or one or two or more of scandium, yttrium, lanthanum, cerium, neodymium, ytterbium and lutetium are added into silver or copper, high-temperature smelting is carried out at the smelting temperature of 1030-1450 ℃, the alloy is atomized into the silver metal alloy powder or the copper metal alloy powder by using high-pressure water after the alloy is fully alloyed, and then the silver metal alloy powder or the copper metal alloy powder is dried and sieved by a sieve of 50-500 meshes.
Step 1-1 preparation of silver Metal alloy powder
When the silver metal alloy powder is prepared, silver, added metal elements and rare earth elements are subjected to high-temperature smelting at the smelting temperature of 1030-1400 ℃, alloyed, atomized into silver alloy powder by using high-pressure water, dried and sieved by a 200-mesh sieve, wherein the raw materials are calculated according to the mass percentage: 98.5 percent of silver, 0.3 percent of rare earth yttrium cerium alloy, 1 percent of indium and 0.2 percent of nickel.
Step 1-2 preparation of copper metal alloy powder
When copper metal alloy powder is prepared, copper, added metal elements and rare earth elements are subjected to high-temperature smelting at the smelting temperature of 1030-1400 ℃, alloyed, atomized into copper alloy powder by using high-pressure water, dried and sieved by a 200-mesh sieve, wherein the raw materials are calculated according to the mass percentage: 99.05% of copper, 0.6% of rare earth lanthanum, yttrium and cerium alloy, 0.15% of bismuth and 0.2% of nickel.
And 2, roasting and oxidizing the silver metal alloy powder to obtain silver metal oxide powder, wherein the oxidation temperature is 600 ℃, the oxygen pressure is 3Mpa, and the time is 10 hours.
And 3, adding graphite, nickel, silicon carbide, yttrium, lanthanum oxide and diamond micro powder into the silver metal alloy powder obtained in the step 2, and uniformly mixing the silver metal alloy powder, the nickel 10%, the diamond 1%, the lanthanum oxide 0.2% and the other 0.5% in a powder mixing ball mill for 8 hours, wherein the ball-to-material ratio is 20: 1.
And 4, molding and sintering the mixture obtained in the step 3 to obtain an ingot blank. The isostatic pressing primary blank molding pressure is 180Mpa, the density is controlled to be 75-90% of the theoretical density, the primary blank is placed into a sintering furnace, then the primary blank is vacuumized and filled with inert gas for protection, the sintering temperature is 900 ℃, the sintering time is 3 hours, and then the primary blank is cooled to below 50 ℃ along with the furnace and taken out of the furnace.
And 5, carrying out re-pressing, extruding and rolling on the obtained ingot blank. And (3) after the ingot blank is re-pressed, extruding the ingot blank into a strip, and then rolling the strip to obtain the silver alloy layer electrical contact material containing the additive or the metal oxide for later use. The extrusion temperature was 880 ℃ and the extrusion ratio was 100.
And 6, preparing the copper alloy layer strip according to the same steps of the steps 2, 3, 4 and 5, wherein the final content is as follows: 1% of diamond micro powder, 0.9% of lanthanum, yttrium and cerium, 0.15% of bismuth, 0.2% of nickel, 96.75% of copper and 1% of others.
And 7, adopting amorphous brazing filler metal for the brazing filler metal layer, and adopting a smelting method for the preparation process. The strip material is prepared for standby through extrusion, rolling and annealing processes.
And 8, respectively polishing the composite surfaces of the silver alloy, the copper alloy and the brazing filler metal strip containing the additives, and then respectively or simultaneously compounding the composite surfaces on thermal compounding equipment, wherein the compounding temperature is 830 ℃, and the speed is 4 m/min.
And 9, preparing the strip subjected to thermal compounding into the silver-saving and environment-friendly three-layer composite contact through cold rolling, punching and the like. In the processing process, protective gas is used for protection when the strip is subjected to heat preservation and annealing, the temperature is 600 ℃, the time is 2 hours, and the rolling quantity of each pass is less than 20% during cold rolling.
Example two:
the difference from the first embodiment is that:
and step 3: adding graphite, nickel, silicon carbide, yttrium, lanthanum oxide and diamond micro powder into the silver metal alloy powder obtained in the step 2, and uniformly mixing the silver metal alloy powder, the nickel, the diamond, the lanthanum oxide, the yttrium, the aluminum oxide and the zirconium oxide in a powder mixing ball mill according to the proportion of 90% of the silver metal alloy, 5.7% of the nickel, 1.2% of the diamond, 1.5% of the lanthanum oxide, 0.5% of the yttrium, 0.2% of the aluminum oxide, 0.1% of the zirconium oxide and 0.8% of the bismuth oxide, wherein the powder mixing time is 8 hours, and the ball-.
And 6, preparing the copper alloy layer strip according to the same steps of the steps 2, 3, 4 and 5, wherein the final content is as follows: copper: 89%, nickel 3.7%, diamond 1.5%, lanthanum oxide 1.5%, yttrium 0.5%, scandium oxide 0.5%, zinc oxide 1%, aluminum oxide 0.1%, zirconium oxide 0.3%, bismuth oxide 1%, lanthanum yttrium cerium alloy 0.9%.
EXAMPLE III
The difference from the first embodiment is that:
and step 3: adding graphite, nickel, silicon carbide, yttrium, lanthanum oxide and diamond micro powder into the silver metal alloy powder obtained in the step 2, and uniformly mixing the silver metal alloy powder, the nickel and the diamond micro powder according to the proportion of 96% of silver metal alloy, 0.5% of nickel, 1.5% of diamond and 2% of lanthanum oxide in a powder mixing ball mill, wherein the powder mixing time is 8 hours, and the ball-to-material ratio is 20: 1.
And 6, preparing the copper alloy layer strip according to the same steps of the steps 2, 3, 4 and 5, wherein the final content is as follows: copper: 90%, 3% of nickel, 1% of vanadium, 0.5% of manganese, 1% of zinc oxide, 1% of titanium dioxide, 0.5% of diamond, 1.5% of lanthanum oxide, 0.9% of lanthanum-yttrium-cerium alloy, 0.1% of scandium and 1% of the rest.
The three-layer composite material containing the additives prepared by the method has the following main properties:
1. density: not less than 8.3g/cm 3;
2. the Hardness (HB) is more than or equal to 70;
3. resistivity: less than or equal to 2.15 mu omega cm;
the above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (4)
1. A preparation method of a layered silver-copper-brazing three-composite electrical contact material prepared by an atomization method is characterized by comprising the following steps of: comprises that
Step 1: preparing silver alloy powder and copper alloy powder by adopting an atomization method, and preparing brazing filler metal by adopting a smelting method;
step 2: carrying out oxidation treatment on the silver alloy powder and the copper alloy powder to obtain silver oxide alloy powder and copper oxide alloy powder;
and step 3: adding an additive into the silver alloy powder and the copper alloy powder obtained in the step 2 by adopting a powder mixing method, and mixing with an abrasive to respectively obtain silver alloy mixed powder and copper alloy mixed powder;
and 4, step 4: respectively molding and sintering the silver alloy mixed powder and the copper alloy mixed powder to obtain a silver alloy layer ingot blank and a copper alloy layer ingot blank;
and 5: re-pressing, extruding and rolling the obtained silver alloy layer ingot blank and the copper alloy layer ingot blank to obtain a silver alloy layer strip and a copper alloy layer strip;
step 6: preparing brazing filler metal into brazing filler metal layer strips;
and 7: sequentially overlapping the silver alloy layer strip, the copper alloy layer strip and the brazing filler metal strip together for thermal compounding;
and 8: preparing the hot-compounded strip into a three-layer composite contact through cold rolling and punching processes;
in the step 5, the extrusion temperature is 880 ℃, and the extrusion ratio is 100;
in the step 7, the compounding temperature is 800-850 ℃, and the speed is 3-5 m/min;
in the step 8, the strip subjected to thermal compounding is subjected to heat preservation annealing, and is protected by protective gas at the temperature of 500-650 ℃ for 1-3 hours, wherein the rolling amount of each pass is less than 20% during cold rolling;
adding metal elements and rare earth elements into silver, smelting at a high temperature of 1030-1400 ℃, atomizing the silver alloy powder into silver alloy powder by using high-pressure water after alloying, drying and sieving the silver alloy powder by using a sieve of 150-250 meshes to obtain the silver alloy powder;
adding metal elements and rare earth elements into copper, smelting at a high temperature of 1030-1400 ℃, atomizing the copper alloy powder into copper alloy powder by using high-pressure water after alloying, drying and sieving by using a sieve of 150-250 meshes to obtain the copper alloy powder;
the oxidation temperature in the step 2 is 500-700 ℃, the oxygen pressure is 1-3 Mpa, and the time is 5-15 hours;
the additive in the step 3 is at least one of metal oxide, nonmetal and nonmetal compound, the mixing mode is ball milling, the powder mixing time is 6-10 hours, and the ball material ratio is 15-25: 1;
in the step 4, the isostatic pressing primary blank is molded under the pressure of 150-180 MPa, the density is controlled to be 75-90% of the theoretical density, the primary blank is placed into a sintering furnace, then the primary blank is vacuumized and filled with inert gas for protection, the sintering temperature is 800-1000 ℃, the time is 2-5 hours, and then the primary blank is cooled to below 50 ℃ along with the furnace and taken out of the furnace;
in the step 1, the silver alloy powder comprises the following raw materials in percentage by mass: 98.5 percent of silver, 0.3 percent of rare earth yttrium cerium alloy, 1 percent of indium and 0.2 percent of nickel;
in the step 1, the copper alloy powder comprises the following raw materials in percentage by mass: 99.05% of copper, 0.6% of rare earth lanthanum, yttrium and cerium alloy, 0.15% of bismuth and 0.2% of nickel.
2. The preparation method of the layered silver-copper-brazing-filler-metal three-composite electrical contact material prepared by the atomization method according to claim 1, which comprises the following steps: the method is characterized in that: in the step 3, the nonmetal is at least one of diamond, graphite, boron, silicon and phosphorus, and the nonmetal compound is at least one of a compound of boron, silicon and phosphorus and silicon carbide.
3. The preparation method of the layered silver-copper-brazing-filler-metal three-composite electrical contact material prepared by the atomization method according to claim 1, which comprises the following steps:
the metal oxide in the step 3 is SnO2、ZnO、CuO、Fe2O3、CdO、In2O3、Bi2O3、Al2O3、MoO3、ZrO2At least one of them.
4. A material produced by the production method according to any one of claims 1 to 3.
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| CN108220650A (en) * | 2017-12-27 | 2018-06-29 | 昆明贵金属研究所 | A kind of multicomponent oxide enhancing silver-based electric contact material and preparation method thereof |
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| CN114914109B (en) * | 2022-04-26 | 2023-03-28 | 浙江省冶金研究院有限公司 | Preparation method of copper-chromium-tellurium-copper-chromium composite contact |
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Denomination of invention: A kind of layered silver copper brazing three composite electrical contact material prepared by atomization method Effective date of registration: 20201126 Granted publication date: 20191220 Pledgee: China Co. truction Bank Corp Yueqing branch Pledgor: WENZHOU LONGSUN ELECTRICAL ALLOY Co.,Ltd. Registration number: Y2020330001038 |
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Date of cancellation: 20230615 Granted publication date: 20191220 Pledgee: China Co. truction Bank Corp Yueqing branch Pledgor: WENZHOU LONGSUN ELECTRICAL ALLOY Co.,Ltd. Registration number: Y2020330001038 |