CN112725652B - Silver zinc oxide electric contact material and preparation method thereof - Google Patents
Silver zinc oxide electric contact material and preparation method thereof Download PDFInfo
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- CN112725652B CN112725652B CN202011547947.6A CN202011547947A CN112725652B CN 112725652 B CN112725652 B CN 112725652B CN 202011547947 A CN202011547947 A CN 202011547947A CN 112725652 B CN112725652 B CN 112725652B
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- 239000000463 material Substances 0.000 title claims abstract description 54
- DUCFBDUJLLKKPR-UHFFFAOYSA-N [O--].[Zn++].[Ag+] Chemical compound [O--].[Zn++].[Ag+] DUCFBDUJLLKKPR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000005491 wire drawing Methods 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 6
- 230000004927 fusion Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003466 welding Methods 0.000 abstract description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- 230000003628 erosive effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000004080 punching Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Contacts (AREA)
- Manufacture Of Switches (AREA)
Abstract
The invention discloses a silver zinc oxide electrical contact material and a preparation method thereof, wherein the silver zinc oxide electrical contact material comprises Ag86.5-92 wt.%, ZnO 5-10 wt.%, and SnO22～3wt.％，CuO 1～3wt.％，Li20.5-2 wt.% of O and 0.5-2 wt.% of other additives, and the preparation method comprises the following steps: firstly, preparing an AgZn alloy spindle by utilizing Ag ingot, Zn ingot, Sn, Cu, Li and additives, turning a surface skin, heating and extruding into a wire material, drawing to the diameter of 2.0mm, punching into a broken wire, oxidizing, pressing into an ingot, sintering, hot extruding, drawing and the like, and finally preparing a finished wire material. The invention has the advantages that: by adding Li, Cu and Sn elements into the material, finer spherical oxide particles are obtained, and meanwhile, the oxide particles are dispersed and distributed on the Ag matrix, so that the density of the material is improved, and the arc erosion resistance and the fusion welding resistance of the material are increased. Meanwhile, the manufactured wire is used for manufacturing a rivet contact, the cracking proportion of the rivet in the cold heading process is obviously reduced, the obtained electric service life can reach more than 10 ten thousand times under the direct current or alternating current condition, and the rivet contact has higher burning loss resistance and longer electric service life.
Description
Technical Field
The invention belongs to the field of manufacturing of electrical materials, and particularly relates to a silver zinc oxide electrical contact material and a preparation method thereof.
Background
Silver-based electrical contact materials have excellent electrical and thermal conductivity, and due to the low hardness and poor resistance to electrical wear of pure silver, it is usually necessary to add other additives to the silver matrix to enhance the electrical properties of the material, such as the welding resistance, electrical life, and resistance to arc burning of the contacts. The silver zinc oxide (AgZnO) is one of the silver zinc oxide and the AgZnO, has better fusion welding resistance and arc erosion resistance, and can be applied to power relays and general relays. The main methods for preparing AgZnO at present comprise a powder metallurgy method, an alloy internal oxidation method and an atomization process, wherein the atomization process is to atomize alloy melt into powder by air or cooling water, prepare alloy oxidation powder by powder preoxidation and high-temperature oxidation processes, and finally press-form the powder to prepare an electrical contact material; the alloy internal oxidation method is used for preparing the electric contact material by alloy fusion casting and alloy oxidation. However, the electric contact materials manufactured by the processes have the problems of small material density, cracking during cold heading forming of contact rivets and influence on the service performance of the materials, and in addition, the conventional materials have low sintering density and need to be improved in the formula or manufacturing process of the conventional electric contact materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the silver zinc oxide electric contact material and the preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is a preparation method of a silver zinc oxide electric contact material, which is characterized by comprising the following steps:
(1) preparing a smelting alloy ingot: according to the formula of the silver zinc oxide electric contact material, adding an Ag plate, a Zn plate and additives, wherein the additives are Li, Cu and Sn, smelting AgZn alloy in advance, and casting the solution into a mold to prepare an AgZn alloy spindle;
(2) turning treatment: removing a layer of oxide skin on the surface of a cast AgZn alloy ingot by using a lathe, wherein the lower amount of a single side lathe is 1-2 mm;
(3) and (3) extrusion treatment: preheating the turned ingot blank at 700 +/-10 ℃, and then loading the ingot blank into an oil pressure extruder at the temperature to extrude the ingot blank into a first wire material;
(4) drawing and cutting; according to the drawing process, the first wire is drawn into a second wire with smaller diameter by a drawing machine, and then the second wire is cut into small sections.
(5) Internal oxidation: adding the cut small material sections into an internal oxidation furnace, introducing oxygen, starting the oxidation furnace, heating to 800 ℃ at 700-;
(6) and (3) ingot pressing treatment: pressing the oxidized material section into an AgZnO ingot blank by using a hydraulic press, wherein the pressure of the hydraulic press is 30 +/-2 MPa;
(7) sintering treatment: placing the AgZnO ingot blank into a sintering furnace, and sintering at 700-800 ℃ for 2-6 h;
(8) extruding: heating the sintered AgZnO spindle at the temperature of 700-800 ℃ for 3-5 hours, and then forming the sintered AgZnO spindle into a semi-finished wire by using an extruder;
(9) drawing treatment: according to the drawing process, the semi-finished wire is drawn into a finished wire with smaller diameter by a medium-frequency wire drawing machine.
Further setting the ingot pressing pressure maintaining time of the step (6) to be 15 s.
Further setting the process parameters of the medium-frequency wire drawing machine in the drawing process of the step (9) as wire drawing speed 4.5Hz and current intensity 12A.
The invention also provides a silver zinc oxide electrical contact material which comprises the following components in percentage by weight:
Ag 83.5～91.5wt.％，ZnO 5～10wt.％，SnO2 2～3wt.％，CuO 0.5～1wt.％，Li20.5-1 wt.% of O and 0.5-1.5 wt.% of other additives, wherein the other additives refer to elements such as Ni and Te.
The invention can achieve the following beneficial effects:
(1) compared with the existing silver zinc oxide material, the method for adding the elements Li, Cu and Sn has the advantages that the addition of the element Li is to activate the sintering process of AgZnO, so that the compactness of the material is improved, ZnO particles in the material are spherical, meanwhile, trace Sn can enable the oxide particles to be finer, the Cu element can enable the oxide particles to be dispersedly distributed on a silver substrate, the influence of a flaky structure in the original AgZnO material on the electrical property can be eliminated under the combined action of the Sn and Cu elements, the fusion welding resistance and the burning resistance of the material are improved under the combined action of the three trace elements, and the electrical life of the material is further prolonged;
(2) the shape and distribution of oxide particles in the material and the compactness of the material are improved, so that the cracking proportion of the rivet contact during forming is further reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples.
Example 1:
(1) preparing a smelting alloy ingot: manufacturing according to 25kg in a 1 furnace, firstly putting 86 wt.% of Ag plate, 9.5 wt.% of Zn plate, 2 wt.% of Sn, 1 wt.% of Cu, 1 wt.% of Li and 0.5 wt.% of additives, smelting in a medium-frequency smelting furnace, setting the smelting temperature at 1200 ℃, smelting for 0.5h, stirring by using a graphite rod in the smelting process, then reducing the temperature to 1100 ℃ for refining for 12min, finally pouring the refined alloy melt into a mold, putting the mold into water for cooling after solidification, and finally manufacturing an AgZn alloy spindle;
(2) turning treatment: removing a layer of oxide skin on the surface of the cast alloy ingot by using a lathe, wherein the quantity of the single side lathe is 1-2mm, and the rotating speed of the lathe is 2000 rpm;
(3) and (3) extrusion treatment: preheating the turned ingot blank at 700 +/-10 ℃, and then loading the ingot blank into an oil pressure extruder at the temperature to extrude the ingot blank into 6.0mm phi wires;
(4) drawing and cutting; according to the drawing process, drawing the wire with the diameter of 6.0mm into the wire with the diameter of 2.0mm by a wire drawing machine, and cutting the wire with the diameter of 2.0mm into small sections with the diameter of 10-15mm by a punch.
(5) Internal oxidation: adding the cut small material sections into an internal oxidation furnace, introducing oxygen, starting the oxidation furnace, heating to 800 ℃ at 700-;
(6) and (3) ingot pressing treatment: pressing the oxidized material section into a spindle with the diameter of phi 90mm by using a hydraulic machine, wherein the pressure of the hydraulic machine is 30 +/-2 MPa;
(7) sintering treatment: putting the ingot blank into a sintering furnace, and sintering at 700-800 ℃ for 2-6 h;
(8) extruding: heating the sintered AgZnO spindle at 800 ℃ at 700-;
(9) drawing treatment: according to the drawing process, drawing the wire with the diameter of 6mm into the wire with the diameter of 1.88mm by a medium-frequency wire drawing machine, wherein the drawing process comprises the following steps:
Φ6.0Δ→→Φ5.6→→Φ5.2→→Φ4.9Δ→→Φ4.5→→Φ4.2Δ→→Φ3.9→→Φ3.6→→Φ3.4Δ→→Φ3.2→→Φ3.0→→Φ2.9Δ→→Φ2.7→→Φ2.5→→Φ2.3Δ→→Φ2.1→→Φ2.0→→Φ1.88
Δ represents annealing, annealing temperature: keeping the temperature at 850 +/-10 ℃ for 2-6 h, and annealing in air. Wherein "→ →" represents hot drawing and "→" represents cold drawing.
The process parameters of the medium-frequency wire drawing machine in the drawing process are wire drawing frequency of 5.0Hz and current intensity of 10A; example 2:
the difference from example 1 was that, in the case of the charge of raw materials, 88.5 wt.% Ag plate and 7 wt.% Zn plate, and 2 wt.% Sn, 1 wt.% Cu, 1 wt.% Li, and 0.5 wt.% additive were charged in accordance with the configuration of 1 furnace of 25 kg.
Example 3:
the difference from examples 1 and 2 is that the charge of raw materials was varied in the amount of 1 furnace 25kg, 90.5 wt.% Ag plate and 5 wt.% Zn plate, and 2 wt.% Sn, 1 wt.% Cu, 1 wt.% Li, and 0.5 wt.% of additives.
The AgZnO/Cu rivet contact prepared by the above embodiment is used for carrying out simulated electrical property experiments, and the specifications of the rivet are moving contact R3.2x1.4(0.5) +1.5x1.2SR20 and static contact F3.2x1.4(0.5) +1.5x 2.5. The experimental conditions for simulating the electrical properties are as follows: 250VAC, 10A, closing force of 100g, breaking force of 60g and contact frequency of 90 times/min; 20VDC, 9A, 100g closing force, 50g breaking force and 90 contact frequencies/min, and the experimental results are shown in Table 1.
TABLE 1 Electrical Performance test results for AgZnO/Cu rivet contacts
The experimental results show that the electrical property of the example 2 in the three examples is the best, and compared with the comparative example, the electrical property of the material has good performance under both direct current conditions and alternating current conditions, the contact resistance is low, the electrical life exceeds 11 ten thousand times, and the electrical life of other examples reaches more than 9.9 ten thousand times, which is mainly attributed to the fact that the Li element is added in the invention, the electrical life of the material can be effectively prolonged, and the tissue of the prepared wire material and even the prepared rivet contact material is effectively improved.
By adopting the technical scheme, the invention can obtain the following technical effects:
(1) compared with the traditional silver zinc oxide formula, the contact made of the material produced by the invention has better electric service life under the direct current condition, and the material has the advantages of longer service life of more than 10 ten thousand times under a certain current through testing, higher fusion welding resistance and burning loss resistance;
(2) by adding Li element into the material, the density of the material is improved, and the plastic deformation capacity of the material is improved;
(3) the rivet made of the wire material prepared by the invention has the electric service life of more than 10 ten thousand times, has lower contact resistance, the lowest contact resistance is 0.5m omega, and the highest electric service life can reach about 11 ten thousand times.
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 (3)
1. The preparation method of the silver zinc oxide electric contact material is characterized by comprising the following steps:
(1) preparing a smelting alloy ingot: according to the formula of the silver zinc oxide electric contact material, adding an Ag plate, a Zn plate and additives, wherein the additives are Li, Cu, Sn and other additives, smelting AgZn alloy in advance, casting the molten liquid into a mold to prepare an AgZn alloy spindle, and the mass ratio of the materials added is as follows: 88.5 wt% Ag plate, 7wt% Zn plate, 2wt% Sn, 1wt% Cu, 1wt% Li and 0.5wt% other additives, wherein the other additives are Ni or Te;
(2) turning treatment: removing a layer of oxide skin on the surface of a cast AgZn alloy ingot by using a lathe, wherein the lower amount of a single side lathe is 1-2 mm;
(3) and (3) extrusion treatment: preheating the turned ingot blank at 700 +/-10 ℃, and then loading the ingot blank into an oil pressure extruder at the temperature to extrude the ingot blank into a first wire material;
(4) drawing and cutting; according to the drawing process, the first wire is drawn into a second wire with smaller diameter by a wire drawing machine, and then the second wire is cut into small sections;
(5) internal oxidation: adding the cut small material sections into an internal oxidation furnace, introducing oxygen, starting the oxidation furnace, heating to 800 ℃ for 20-30 hours at the oxygen pressure of 0.4-0.8MPa, and taking out the material after the oxidation is finished to prepare for ingot pressing;
(6) and (3) ingot pressing treatment: pressing the oxidized material section into an AgZnO ingot blank by using a hydraulic press, wherein the pressure of the hydraulic press is 30 +/-2 MPa;
(7) sintering treatment: placing the AgZnO ingot blank into a sintering furnace, and sintering at 700-800 ℃ for 2-6 h;
(8) extruding: heating the sintered AgZnO spindle at the temperature of 700-800 ℃ for 3-5 hours, and then forming the sintered AgZnO spindle into a semi-finished wire by using an extruder;
(9) drawing treatment: according to the drawing process, the semi-finished wire is drawn into a finished wire with smaller diameter by a medium-frequency wire drawing machine.
2. The method of claim 1, wherein: and (4) the ingot pressing pressure maintaining time of the step (6) is 15 s.
3. The method of claim 1, wherein: and (4) the process parameters of the intermediate frequency wire drawing machine in the drawing process of the step (9) are wire drawing frequency of 4.5Hz and current intensity of 12A.
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| CN110951980A (en) * | 2019-11-27 | 2020-04-03 | 福达合金材料股份有限公司 | Method for preparing silver metal oxide electric contact material by internal oxidation method for improving fusion welding resistance |
| CN111118332A (en) * | 2019-12-26 | 2020-05-08 | 福达合金材料股份有限公司 | Dynamic internal oxidation method for silver-based metal oxide electrical contact material |
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