CN103205595B - Novel silver-based electrical contact material and preparation method thereof - Google Patents
Novel silver-based electrical contact material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 title abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000004332 silver Substances 0.000 title abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- 238000009749 continuous casting Methods 0.000 claims abstract description 22
- 238000005266 casting Methods 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 32
- 238000005097 cold rolling Methods 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000007669 thermal treatment Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000010923 batch production Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000003466 welding Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007600 charging Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention discloses a novel silver-based electrical contact material and a preparation method thereof. The material comprises the following components: 3wt%-6wt% of Cu, 0.3wt%-0.6wt% of Ni, 0.05wt%-0.1wt% of Al and the balance of Ag. The electrical contact material with uniform chemical composition (without Cu, Ni aggregation) is prepared by a continuous casting, which can realize continuous charging, melting, casting and scale batch production. A slab has oxygen content no more than 10PPM, no defects like oxide, inclusion and shrinkage, high yield and low production cost. The AgCuNiAl alloy from mass production has uniform composition and good performance consistency; and after subsequent processing and an internal oxidation treatment, the strip has small difference between transverse and longitudinal properties, so as to improve the comprehensive performance of the material. The silver-based electric contact material provided by the invention still maintains good flexibility and high temperature strength at 250 DEG C, and has low contact resistance, strong fusion welding resistance and arc erosion resistance. The novel silver-based electric contact material can be used as a thermosensitive fuse elastic contact material in light and middle load conditions, and can effectively prevent welding and adhesion of the contact points, prolong the service life and improve reliability of the material.
Description
Technical field
The present invention relates to metal material field, particularly relate to internal oxidition type AgCuNiAl alloy contact material and continuous casting preparation method thereof.
background technology
Silver-based electric contact material is widely applied due to features such as low, the anti-melting welding ability of its contact resistance are strong, abrasion resistance properties is good, anti-electroerosion ability is strong, silver and silver alloys are the primary electrical contact materials of the contacts such as electric switch, instrument, instrument, and contact material performance quality directly has influence on electrical equipment, the performance of instrument and life-span.Usually adopt after being frozen into rectangle ingot by stove casting both at home and abroad, milling train is adopted to be processed into sheet material, then the method for internal oxidition prepares AgCuONiO alloy sheet product, this type of by stove melting method to equipment and operator require high, batch production material composition, consistency of performance is poor, production efficiency is low, production cost is high, is difficult to produce in enormous quantities, affects the application of material large-scale popularization.
summary of the invention
The object of the invention is contact material of openly a kind of internal oxidition type AgCuNiAl alloy and preparation method thereof, the AgCuNiAl alloy contact material chemical composition that the present invention adopts continuous metal cast process to produce is evenly (without Cu, Ni assembles), can continuous charging, melting and casting, realize mass-producing batch production, slab oxygen level≤10PPM, oxide-free, inclusion, the defects such as shrinkage cavity, yield rate is high, production cost is low, produce AgCuNiAl alloying constituent in enormous quantities even, performance is unanimously good, after following process and internal oxidition process, laterally longitudinal performance difference is little for band, greatly improve material over-all properties.
The chemical composition of AgCuNiAl alloy material of the present invention is: Cu3wt% ~ 6wt%, Ni0.3wt% ~ 0.6wt%, Al0.05wt% ~ 0.1wt%, and surplus is Ag.The feature of this material is, because Ni is insoluble in Ag, rely on Cu to be brought in alloy by Ni to go, and the content of Cu is lower, be not enough to Ni to be added to uniformly in matrix Ag, in the alloy prepared by ordinary method, Ni easily produces gathering, cause material chemical composition segregation serious, homogeneity is poor, batch production performance consistence is poor, be difficult to produce product stable and reliable for performance in enormous quantities, and trace of Al is fused in Ag admittedly, because Al is oxidizable, in AgCuNiAl alloy inner oxidation process, preferential oxidation, thus stop CuO, NiO oxidation is assembled mutually, promote internal oxidition process, improve alloy strength.
Processing step of the present invention is as follows:
With purity Ag >=99.99%, Cu >=99.99%, Ni >=99.95%, Al >=99.99% for raw material, by Cu3wt% ~ 6wt%, Ni0.3wt% ~ 0.6wt%, Al0.05wt% ~ 0.1wt%, surplus is that Ag mass percent is prepared burden, Cu0.1%, Ni0.04% of the oxidizable scaling loss of suitable increase, be prepared as follows:
1. first by Cu, Ni, Al (vacuum tightness>=10 in vacuum oven
-1mPa) founding becomes master alloy ingot casting;
2. CuNiAl master alloy ingot rolling is become thickness 3 ~ 5 millimeters of sheet materials and shear and be divided into 4 parts, Ag raw material is divided into 5 parts;
3. after continuous casting furnace being warming up to 700 DEG C ~ 900 DEG C, add a Ag raw material, after Ag melting sources, pass into purity >=99.999% argon gas in stove to stir, add a CuNiAl master alloy, add Ag raw material again after to be melted, after fusing, add a CuNiAl master alloy, so alternately add raw material until add 5 parts of Ag raw materials, 4 parts of CuNiAl master alloys add insulating covering agent;
4. after metal melts completely, refining 30min ~ 60min, start continuous casting, continuous casting steel billet is thickness 8mm, width 160mm; Cast a stove as need founding be continued, in stove, stayed part metals material, stop casting, then by 1. 2. 3. step is reinforced, insulation refining, then start continuous casting, so repeatedly, until cast all alloy raw materials;
5. cold rolling cogging: the cogging of employing two-roller mill, pass deformation control 10% ~ 15%, are cold-rolled to thickness 2.5 millimeters.
6. internal oxidition thermal treatment: 600 ~ 700 DEG C/8 ~ 12h;
7. removing surface: with machinery and labor cleaning surface;
8. intermediate rolling: cold rolling with four-high mill, pass deformation controls 3% ~ 10%, is cold-rolled to thickness 0.6 millimeter;
9. thermal treatment: 600 ~ 700 DEG C/4 ~ 6h;
10. finish rolling: cold rolling with four-high mill, pass deformation controls 3% ~ 6%, is cold-rolled to thickness 0.076 ~ 0.1 millimeter.
AgCuNiAl alloy is after internal oxidition, CuO, NiO, Al2O3 are oxidized phase Dispersed precipitate in matrix phase, alloy plays strengthening effect, simultaneously, oxide compound is on good terms the resistance to galvanic corrosion significantly improving alloy material, anti-melting welding, abrasion resistance properties, has a wide range of applications in delicate electronic device field.But due to the skewness in Ag of the Ni in this alloy, easily assemble, thus cause the consistency of performance of material poor, have impact on this material large-scale production and application.The present invention proposes to add trace metal Al in the alloy, and Al is evenly distributed in Ag matrix, and except alloy strength after raising internal oxidition (see table 3), preferential oxidation in AgCuNi alloy inner oxidation process, stops CuO, NiO oxidation to be assembled mutually; The method of continuous caster melting continuous casting (abbreviation continuous casting) is adopted to produce AgCuNiAl slab; can continuous charging, melting and casting, realize mass-producing batch production; the defect such as slab oxide-free, inclusion, shrinkage cavity; yield rate is high; reduce production cost, alloying constituent is even, and Cu, Ni and trace of Al are evenly distributed in Ag matrix; produce AgCuNiAl alloy property in enormous quantities unanimously good, steady quality is reliable.
The present invention adopts the advantage of the band prepared by continuous cast method to be, and 1. alloy composition is even, strand composition is controlled, can control Cu content in alloy: 3wt% ~ 6wt%, Cu error ± 0.4%, Ni content: 0.3wt% ~ 0.6wt%, Ni error ± 0.05%; Al0.05wt% ~ 0.1wt%; 2. the band oxygen level≤10PPM prepared, the defect such as oxide-free, inclusion, shrinkage cavity, horizontal and vertical performance difference is little, and batch production material composition, consistency of performance are good; 3. can produce (100 kilograms to several tons) without shrinkage cavity by extensive continuous casting continuously, greatly improve the production efficiency of this material and reduce production cost, promoting applying of AgCuNiAl alloy product; 4. electric contact elastic material of the present invention is not containing toxic element such as Pb, Cd, belongs to green material.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment one: with purity Ag >=99.99%, Cu >=99.99%, Ni >=99.95%, Al >=99.99% for raw material, by Cu4.1%wt%, Ni0.34%wt%, Al0.07wt%, surplus is that Ag mass percent is prepared burden, and is prepared as follows:
1, first by Cu, Ni, Al (vacuum tightness>=10 in vacuum oven
-1mPa) founding becomes master alloy ingot casting;
2, CuNiAl master alloy ingot rolling is become thickness 3 ~ 5 millimeters of sheet materials and shear and be divided into 4 parts, Ag raw material is divided into 5 parts;
3, after continuous casting furnace being warming up to 700 DEG C ~ 900 DEG C, add a Ag raw material, after Ag melting sources, in stove, pass into purity >=99.999% argon gas stir, add a CuNiAl master alloy, after to be melted, add Ag raw material again, after fusing, add a CuNiAl master alloy, so alternately add raw material (4 parts of CuNiAl master alloys, 5 parts of Ag raw materials, every stove feeding quantity is at 100-200 kilogram) until add, add insulating covering agent;
4, after metal melts completely, refining 30min ~ 60min, start continuous casting, casting speed is (50mm/min ~ 80mm/min), and continuous casting steel billet is thickness 8mm width 160mm;
5, the cogging of employing two-roller mill, pass deformation control 10% ~ 15%, and thickness 8mm bar plate cold rolling is to thickness 2.5 millimeters.
6,600 ~ 700 DEG C of internal oxidition thermal treatment 8 ~ 12h;
7, with machinery and labor cleaning surperficial;
8, cold rolling with four-high mill, pass deformation controls 3% ~ 10%, is cold-rolled to thickness 0.6 millimeter;
9,600 ~ 700 DEG C of internal oxidition thermal treatment 4 ~ 6h;
10, cold rolling with four-high mill, pass deformation 3% ~ 10%, is rolled to thickness 0.15mm;
11, roll shearing machine cutting edge is used;
12, vacuum annealing temperature 300 DEG C ~ 350 DEG C/3 ~ 4h;
13, use four-high mill finish rolling, pass deformation controls 3% ~ 6%, is cold-rolled to thickness 0.076mm.
14, clean thickness 0.076mm band with gasoline and dry;
15, finished product packing.
Embodiment two: with purity Ag >=99.99%, Cu >=99.99%, Ni >=99.95%, Al >=99.99% for raw material, by Cu5.1wt%, Ni0.44wt%, Al0.07wt%, surplus is that Ag mass percent is prepared burden, and is prepared as follows:
1, first by Cu, Ni, Al (vacuum tightness>=10 in vacuum oven
-1mPa) founding becomes master alloy ingot casting;
2, CuNiAl master alloy ingot rolling is become thickness 3 ~ 5 millimeters of sheet materials and shear and be divided into 4 parts, Ag raw material is divided into 5 parts;
3, after continuous casting furnace being warming up to 700 DEG C ~ 900 DEG C, add a Ag raw material, after Ag melting sources, in stove, pass into purity >=99.999% argon gas stir, add a CuNiAl master alloy, after to be melted, add Ag raw material again, after fusing, add a CuNiAl master alloy, so alternately add raw material (4 parts of CuNiAl master alloys, 5 parts of Ag raw materials, every stove feeding quantity is at 100-200 kilogram) until add, add insulating covering agent;
4, after metal melts completely, refining 30min ~ 60min, start continuous casting, casting speed is (50mm/min ~ 80mm/min), and continuous casting steel billet is thickness 8mm width 160mm;
5, the cogging of employing two-roller mill, pass deformation control 10% ~ 15%, and thickness 8mm bar plate cold rolling is to thickness 2.5 millimeters.
6,600 ~ 700 DEG C of internal oxidition thermal treatment 8 ~ 12h;
7, with machinery and labor cleaning surperficial;
8, cold rolling with four-high mill, pass deformation controls 3% ~ 10%, is cold-rolled to thickness 0.6 millimeter;
9,600 ~ 700 DEG C of internal oxidition thermal treatment 4 ~ 6h;
10, cold rolling with four-high mill, pass deformation 3% ~ 10%, is rolled to thickness 0.15mm;
11, roll shearing machine cutting edge is used;
12, vacuum annealing temperature 300 DEG C ~ 350 DEG C/3 ~ 4h;
13, use four-high mill finish rolling, pass deformation controls 3% ~ 6%, is cold-rolled to thickness 0.085mm.
14, clean thickness 0.085mm band with gasoline and dry;
15, finished product packing.
Embodiment three: with purity Ag >=99.99%, Cu >=99.99%, Ni >=99.95%, Al >=99.99% for raw material, by Cu6.1wt%, Ni0.64wt%, Al0.07wt%, surplus is that Ag mass percent is prepared burden, and is prepared as follows:
1, first by Cu, Ni, Al (vacuum tightness>=10 in vacuum oven
-1mPa) founding becomes master alloy ingot casting;
2, CuNiAl master alloy ingot rolling is become thickness 3 ~ 5 millimeters of sheet materials and shear and be divided into 4 parts, Ag raw material is divided into 5 parts;
3, after continuous casting furnace being warming up to 700 DEG C ~ 900 DEG C, add a Ag raw material, after Ag melting sources, in stove, pass into purity >=99.999% argon gas stir, add a CuNiAl master alloy, after to be melted, add Ag raw material again, after fusing, add a CuNiAl master alloy, so alternately add raw material (4 parts of CuNiAl master alloys, 5 parts of Ag raw materials, every stove feeding quantity is at 100-200 kilogram) until add, add insulating covering agent;
4, after metal melts completely, refining 30min ~ 60min, start continuous casting, casting speed is (50mm/min ~ 80mm/min), and continuous casting steel billet is thickness 8mm width 160mm;
5, the cogging of employing two-roller mill, pass deformation control 10% ~ 15%, and thickness 8mm bar plate cold rolling is to thickness 2.5 millimeters.
6,600 ~ 700 DEG C of internal oxidition thermal treatment 8 ~ 12h;
7, with machinery and labor cleaning surperficial;
8, cold rolling with four-high mill, pass deformation controls 3% ~ 10%, is cold-rolled to thickness 0.6 millimeter;
9,600 ~ 700 DEG C of internal oxidition thermal treatment 4 ~ 6h;
10, cold rolling with four-high mill, pass deformation 3% ~ 10%, is rolled to thickness 0.15mm;
11, roll shearing machine cutting edge is used;
12, vacuum annealing temperature 300 DEG C ~ 350 DEG C 3 ~ 4h;
13, use four-high mill finish rolling, pass deformation controls 3% ~ 6%, is cold-rolled to thickness 0.1mm.
14, clean thickness 0.1mm band with gasoline and dry;
15, finished product packing.
Foreign matter content in the AgCuONiOAl2O3 contact material that embodiment one to three prepares is (mass percent): Fe≤0.001wt%, Sb≤0.001wt%, Bi≤0.001wt%.
The AgCuONiOAl2O3 alloy product chemical composition analysis adopting the embodiment of the present invention one to prepare and performance test data contrast are in table 1, table 2 and table 3.
Table 1 embodiment one AgCuONiOAl2O3 alloy product composition analysis and performance test
As apparent from table 1 data can, the present invention prepare the controlled and horizontal endwise tensile strength of AgCuONiOAl2O3 alloy product composition and unit elongation difference very little.
Table 2AgCuONiO alloy product composition analysis and performance test
Table 3AgCuONiOAl2O3 alloy product composition analysis and performance test
The contrast of contrast table 2 table 3 can be found out, trace of Al adds and significantly improves AgCuONiO alloy material hardness and tensile strength.
Claims (2)
1. a preparation method for the contact material of internal oxidition type AgCuNiAl alloy, is characterized in that containing following processing step:
With purity Ag >=99.99%, Cu >=99.99%, Ni >=99.95%, Al >=99.99% for raw material, by Cu3wt% ~ 6wt%, Ni0.3wt% ~ 0.6wt%, Al0.05wt% ~ 0.1wt%, surplus is that Ag mass percent is prepared burden, Cu0.1%, Ni0.04% of the oxidizable scaling loss of suitable increase, be prepared as follows:
1. first Cu, Ni, Al founding in vacuum oven is become master alloy ingot casting;
2. CuNiAl master alloy ingot rolling is become thickness 3 ~ 5 millimeters of sheet materials and shear and be divided into 4 parts, Ag raw material is divided into 5 parts;
3. after continuous casting furnace being warming up to 700 DEG C ~ 900 DEG C, add a Ag raw material, after Ag melting sources, pass into purity >=99.999% argon gas in stove to stir, add a CuNiAl master alloy, add Ag raw material again after to be melted, after fusing, add a CuNiAl master alloy, so alternately add raw material until add 5 parts of Ag raw materials, 4 parts of CuNiAl master alloys add insulating covering agent;
4. after metal melts completely, refining 30min ~ 60min, start continuous casting, continuous casting steel billet is thickness 8mm, width 160mm; Cast a stove as need founding be continued, in stove, stayed part metals material, stop casting, then by 1. 2. 3. step is reinforced, insulation refining, then start continuous casting, so repeatedly, until cast all alloy raw materials;
5. cold rolling cogging: the cogging of employing two-roller mill, pass deformation control 10% ~ 15%, are cold-rolled to thickness 2.5 millimeters;
6. internal oxidition thermal treatment: 600 ~ 700 DEG C/8 ~ 12h;
7. removing surface: with machinery and labor cleaning surface;
8. intermediate rolling: cold rolling with four-high mill, pass deformation controls 3% ~ 10%, is cold-rolled to thickness 0.6 millimeter;
9. thermal treatment: 600 ~ 700 DEG C/4 ~ 6h;
10. finish rolling: cold rolling with four-high mill, pass deformation controls 3% ~ 6%, is cold-rolled to thickness 0.076 ~ 0.1 millimeter.
2. the preparation method of the contact material of a kind of internal oxidition type AgCuNiAl alloy according to claim 1, is characterized in that the casting speed that 4. described step casts continuously is 50mm/min ~ 80mm/min.
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