CN101608279A - Silver oxide electrical contact material and preparation method thereof - Google Patents
Silver oxide electrical contact material and preparation method thereof Download PDFInfo
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- CN101608279A CN101608279A CNA2009100550602A CN200910055060A CN101608279A CN 101608279 A CN101608279 A CN 101608279A CN A2009100550602 A CNA2009100550602 A CN A2009100550602A CN 200910055060 A CN200910055060 A CN 200910055060A CN 101608279 A CN101608279 A CN 101608279A
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Abstract
The present invention discloses a kind of silver oxide electrical contact material and preparation method thereof, component that described material comprises and weight percent content: SnO
25～12%, ZnO 2～8%, and CuO 0.5～5%, 0.1～1%NiO, 0.1～0.5In
2O
3, 0.1～0.5% Bi
2O
3, the oxide particle granularity is between 0.1～10 μ m, and surplus is Ag.The present invention is owing to adopted heterogeneous enhancing in starting material, comprehensive each wild phase advantage, thereby the processing characteristics that reaches production process is good, the purpose that the material electrical property is good, satisfied the requirement of the compound rivet of high power relay contact, can partly or entirely replace Agcdo to be applied to high power relay, avoid of the pollution of production application process in Agcdo contact environment.
Description
Technical field
What the present invention relates to is a kind of electric contact material and preparation method thereof, and specifically, what relate to is a kind of silver oxide electrical contact material and preparation method thereof.
Background technology
Along with the direction of electric equipment products to large vol, small volume develops, the requirement of electric contact material is improved day by day: it is good to require material under the condition of greatly arc heat and joule heating melting welding, machinery and anti-electric abrasioning performance not to take place; The minimizing metal that produces in breaking course splashes, and shortens the arc time; Under DC environment, resistance fusion welding is good, and material transfer is few, and contact resistance is low and stable.
Though the Agcdo electric contact material that widely uses has fabulous performance and lower material cost at present, especially the high oxidation cadmium content is all the more so, the also very stable maturation of manufacture craft, as described in Chinese patent 95111070, but use more cadmium metal, contain the cadmium oxide compound in the product, in environment, understand residual cadmium salt later on, because cadmium metal and cadmium salt have very big toxic side effect to human body, harmful to environment, trend in the future is to reduce gradually and even stop using the hard contact material that contains cadmium or its compound.
Therefore seek and to substitute the focus that the novel electric contact material of Ag-CdO becomes present domestic and international research.The material system that is hopeful most alternative Ag-CdO material mainly contains Ag-SnO
2, series material such as Ag-ZnO.Specific as follows:
(1) a kind of preparation of silver-tin oxide material CN1425790A
(2) siller tin oxide cupric oxide alloy contact material C N1441071A
(3) silver-tin oxide or indium oxide electric contact wire rod and production technique CN1167835A thereof
(4) method of preparing novel silver tin oxide silk electrical contact material CN101202169A
(5) a kind of preparation method CN10999789A of siller tin oxide electric contact material
(6) siller tin oxide zinc oxide alloy electrical contact and production technique CN1443864A thereof
Document (1) and (4) have been introduced a kind of powder pre-oxidation and have been prepared Ag-SnO
2Method, adopt the AgSnO of this kind method preparation
2Material structure is evenly distributed, and does not have poor tin zone and produces, and its shortcoming is single SnO
2Particle enhanced Ag sill is in use because SnO
2Thereby particle and matrix moistening badness cause the too high problem of temperature rise easily.
Document (2), (3), (5) and (6) have been described at Ag-SnO
2Add in the material as Zn, Cu, various different elements such as La show and add these elements respectively afterwards to AgSnO the influence of material
2The electrical contact performance of material all has improvement in various degree.But because the just adding of trace, thereby can't change Ag-SnO
2The follow-up unmanageable difficult problem of material.
In sum, mainly concentrate on AgSnO about the research that substitutes the AgCdO material both at home and abroad now
2The design of components of material and preparation method develop the AgSnO of a plurality of series
2The no cadmium matrix material of base.But present AgSnO
2Two problems that based composites exists: temperature rise is too high in following process difficulty and the use still is not well solved.
Summary of the invention
The present invention is directed to the above deficiency that prior art exists, a kind of silver oxide alloy electric contact material and preparation method thereof is provided, adopt SnO
2, multiple particle such as ZnO, CuO strengthens the Ag matrix, comprehensively each wild phase advantage makes it not only have the good electrical contact performance, and has good deformation processing performance, and can save the consumption of expensive indium metal.
For achieving the above object, the present invention adopts following technical scheme:
The invention provides a kind of silver oxide alloy electric contact material, component that it comprises and weight percentage are: SnO
25～12%, ZnO 2～8%, and CuO 0.5～5%, 0.1～1%NiO, 0.1～0.5In
2O
3, 0.1～0.5%Bi
2O
3, surplus is Ag.
Described oxide S nO
2, ZnO, CuO, NiO, In
2O
3, Bi
2O
3Average particle size is between 0.1～10 μ m.
The present invention also provides the preparation method of above-mentioned silver oxide alloy electric contact material, may further comprise the steps:
The first step places the smelting furnace melting in proportion with silver ingot and Sn, Cu, Ni, Zn, Bi, In;
Described melting, smelting temperature are between 950-1300 ℃.
In second step, molten metal after the melting is carried out powder by atomization;
Described powder by atomization is to utilize high pressure gas or water slug fused solution metal flow, makes it be atomized into the metal small droplets, obtains powder with postcooling.
In the 3rd step, the powder that obtains atomizing is through preoxidation;
Described preoxidation, wherein gaseous tension is between 0.1～3MPa, and temperature is between 450 ℃～850 ℃, and oxidization time is between 1h～10h;
In the 4th step, powder isostatic pressing after the oxidation is become base substrate;
The described static pressure pressure that waits is between 100～500MPa.
In the 5th step, will wait static pressure to obtain base substrate sintering under oxygen atmosphere;
Described sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
In the 6th step, base substrate behind the sintering is carried out hot pressing;
Described hot pressing temperature is 400～900 ℃, and hot pressing pressure is 300～700MPa, and hot pressing time is 1min～30min.
In the 7th step, base substrate after the hot pressing is carried out resintering;
Described resintering technology is with the 4th step, and promptly sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
In the 8th step, base substrate behind the resintering is carried out hot extrusion obtain wire rod or band.
Described base substrate behind the resintering is carried out hot extrusion, wherein the base substrate Heating temperature is at 600～900 ℃, and extrusion ratio is between 10～400, and extrusion speed is 5～8cm/min, 100～500 ℃ of extrusion mould preheating temperatures.
The present invention adopts the common enhanced material of multivariant oxide wild phase principle of design, and the comprehensive characteristics of each element wild phase obtain that not only electrical contact performance is good, and processing characteristics is good, contact material with low cost.Particularly, the effect of each element is as follows: become SnO after the preoxidation of Sn element
2Particle, arc ablation resistance ability that can strongthener; Zn element preoxidation becoming ZnO particle can be so that material keeps good deformation processing ability when keeping the good resistance heat sealability; The Cu element have the content that helps reduce the In metal, promote the preoxidation of Sn element; A small amount of existence of In element and Bi element can improve the too high problem of temperature rise in the material use, and can reduce preoxidation time; The existence of Ni element can refinement Ag matrix grain, improves mechanics of materials intensity.
Therefore compare with sheet material with existing electrical contact, the present invention is owing to carried out the science design on the starting material component, and adopted the preparation technology who adapts with it, have the good electrical contact performance and satisfied the requirement of high power relay use bimetal composite rivet contact, can partly or entirely replace Agcdo to be applied to high power relay, avoid of the pollution of production application process in Agcdo contact environment.
Description of drawings
Fig. 1 is preparation method's schema in the embodiment of the invention
Embodiment
Below in conjunction with accompanying drawing technical scheme of the present invention is further described, below description just is used to understand the present invention, and is not used in the scope of the present invention that limits.
As shown in Figure 1, the preparation method in following examples of the present invention implements according to the flow process shown in Fig. 1.
Embodiment one
With Ag-5SnO
2-4ZnO-1CuO-0.2NiO-0.3Bi
2O
3-0.5In
2O
3Material preparation is an example
1, take by weighing the 16.8Kg silver ingot, place medium-frequency induction furnace to be warming up to 1000 ℃ of fusings after, add 1Kg Sn, 0.8Kg Zn, 0.2kg Cu, 0.04kg Ni, 0.06kg Bi, 0.1kg In, obtained Ag alloy liquation after the homogenizing through 15 minutes;
2, under 0.5MPa air pressure power, 1200 ℃ of powder by atomizations;
3, atomizing is made powder and pack into and be heated to 600 ℃ of preoxidation in the high pressure vessel, oxygen pressure is 0.1MPa, oxidation 7h;
4, well-oxygenated powder is pressed into base substrate waiting under the static pressure 150MPa;
5, subsequently at 850 ℃ of sintering 5h of oxygen atmosphere;
6, with the base substrate behind the sintering at 750 ℃, hot pressing under the 400MPa pressure, hot pressing time is 10 minutes;
7, then with the hot pressing base substrate at 850 ℃ of resintering 5h of oxygen atmosphere;
8, base substrate behind the resintering is carried out hot extrusion, 800 ℃ of extrusion temperatures, mold preheating temperature are 350 ℃, and extrusion ratio is 250, extrusion speed 5cm/min.
The material property that present embodiment obtained is: tensile strength: 300MPa; Resistivity: 2.12 μ Ω .cm; Hardness: 85HV (annealed state); Density: 9.8g/cm
3The oxide particle mean particle size is 1.5 μ m.
Embodiment two
With Ag-6SnO
2-2ZnO-1.5CuO-0.2NiO-0.3Bi
2O
3-0.1In
2O
3Material preparation is an example
1, takes by weighing the 18Kg silver ingot, melt after placing medium-frequency induction furnace to be warming up to 1000 ℃ of fusings, add 1.2Kg Sn, 0.4Kg Zn, 0.3kg Cu, 0.04kg Ni, 0.06kg Bi, 0.02kg In subsequently successively, after 15 minutes homogenizing, obtain Ag alloy liquation;
2, under the 0.5MPa nitrogen pressure, 1200 ℃ of powder by atomizations;
3, then atomizing being made powder packs into and is heated to 800 ℃, oxidation 5h in the high pressure vessel;
4, well-oxygenated powder is pressed into base substrate waiting under the static pressure 250MPa;
5, subsequently at 800 ℃ of sintering 8h of oxygen atmosphere;
6, with the base substrate behind the sintering at 700 ℃, hot pressing under the 500MPa pressure, hot pressing time is 15 minutes;
7, then with the hot pressing base substrate at 900 ℃ of resintering 5h of oxygen atmosphere;
8, base substrate behind the resintering is carried out hot extrusion, 830 ℃ of extrusion temperatures, mold preheating temperature are 400 ℃, and extrusion ratio is 300, extrusion speed 6cm/min.
The material property that present embodiment obtained is: tensile strength: 310MPa; Resistivity: 2.2 μ Ω .cm; Hardness: 90HV (annealed state); Density: 9.8g/cm
3The oxide particle mean particle size is 1 μ m.
Embodiment three
With Ag-7SnO
2-6ZnO-1CuO-0.5NiO-0.3Bi
2O
3-0.2In
2O
3Material preparation is an example
1, takes by weighing the 17Kg silver ingot, place medium-frequency induction furnace to be warming up to 1000 ℃ of fusings, add 1.4KgSn, 1.2KgZn, 0.2kgCu, 0.1kgNi, 0.06kgBi, 0.04kgIn subsequently successively, obtained Ag alloy liquation through 15 minutes after the homogenizing;
2, under the 0.8MPa nitrogen pressure, 1150 ℃ of powder by atomizations;
3, then atomizing being made powder packs into and is heated to 650 ℃, oxidation 10h in the high pressure vessel;
4, well-oxygenated powder is pressed into base substrate waiting under the static pressure 450MPa;
5, subsequently at 750 ℃ of sintering 8h of oxygen atmosphere;
6, with the base substrate behind the sintering at 650 ℃, hot pressing under the 600MPa pressure, hot pressing time is 20 minutes;
7, then with the hot pressing base substrate at 750 ℃ of resintering 8h of oxygen atmosphere;
8, base substrate behind the resintering is carried out hot extrusion, mold preheating temperature is 450 ℃, 700 ℃ of extrusion temperatures, and extrusion ratio is 150, extrusion speed 5cm/min.
The material property that present embodiment obtained is: tensile strength: 360MPa; Resistivity: 2.4 μ Ω .cm; Hardness: 105HV (annealed state); Density: 9.5g/cm
3The oxide particle mean particle size is 5 μ m.
Embodiment four
With Ag-12SnO
2-2ZnO-5CuO-0.2NiO-0.5Bi
2O
3-0.3In
2O
3Material preparation is an example
1, takes by weighing the 16.8Kg silver ingot, place medium-frequency induction furnace to be warming up to 1000 ℃ of fusings, add 2.0KgSn, 0.6KgZn, 1.0kgCu, 0.04kgNi, 0.1kgBi, 0.06kgIn subsequently successively, obtained Ag alloy liquation through 15 minutes after the homogenizing.
2, under the 2MPa nitrogen pressure, 1050 ℃ of powder by atomizations;
3, then atomizing being made powder packs into and is heated to 500 ℃, oxidation 10h in the high pressure vessel;
4, well-oxygenated powder is pressed into base substrate waiting under the static pressure 300MPa;
5, subsequently at 850 ℃ of sintering 5h of oxygen atmosphere;
6, with the base substrate behind the sintering at 750 ℃, hot pressing under the 400MPa pressure, hot pressing time is 20 minutes;
7, then with the hot pressing base substrate at 850 ℃ of resintering 5h of oxygen atmosphere;
8, base substrate behind the resintering is carried out hot extrusion and obtain the silk material, 600 ℃ of extrusion temperatures, mold preheating temperature are 400 ℃, and extrusion ratio is 100, extrusion speed 5cm/min.
The material property that present embodiment obtained is: tensile strength: 350MPa; Resistivity: 2.42 μ Ω .cm; Hardness: 110HV (annealed state); Density: 9.6g/cm
3The oxide particle mean particle size is 2 μ m.
Embodiment five
With Ag-5SnO
2-2ZnO-0.5CuO-0.1NiO-0.1Bi
2O
3-0.3In
2O
3Material preparation is an example
1, takes by weighing the 17.6Kg silver ingot, place medium-frequency induction furnace to be warming up to 1000 ℃ of fusings, add 1Kg Sn, 0.4KgZn, 0.1kg Cu, 0.02kg Ni, 0.02kg Bi, 0.06kg In subsequently successively, obtained Ag alloy liquation through 15 minutes after the homogenizing.
2, under the 1MPa nitrogen pressure, 1250 ℃ of powder by atomizations;
3, then atomizing being made powder packs into and is heated to 800 ℃, oxidation 3h in the high pressure vessel;
4, well-oxygenated powder is pressed into base substrate waiting under the static pressure 300MPa;
5, subsequently at 850 ℃ of sintering 5h of oxygen atmosphere;
6, with the base substrate behind the sintering at 750 ℃, hot pressing under the 400MPa pressure, hot pressing time is 30 minutes;
7, then with the hot pressing base substrate at 850 ℃ of resintering 5h of oxygen atmosphere;
8, base substrate behind the resintering is carried out hot extrusion and obtain the silk material, 850 ℃ of extrusion temperatures, mold preheating temperature are 450 ℃, and extrusion ratio is 350, extrusion speed 5cm/min.
The material property that present embodiment obtained is: tensile strength: 310MPa; Resistivity: 2.2 μ Ω .cm; Hardness: 95HV (annealed state); Density: 9.6g/cm
3The oxide particle mean particle size is 0.1 μ m.
Embodiment six
With Ag-9SnO
2-2ZnO-4CuO-0.2NiO-0.3Bi
2O
3-0.3In
2O
3Material preparation is an example
1, takes by weighing the 16.8Kg silver ingot, place medium-frequency induction furnace to be warming up to 1000 ℃ of fusings, add 1.8Kg Sn, 0.4Kg Zn, 0.8kg Cu, 0.04kg Ni, 0.06kg Bi, 0.1kg In subsequently successively, obtained Ag alloy liquation through 15 minutes after the homogenizing.
2, under the 3MPa nitrogen pressure, 1100 ℃ of powder by atomizations;
3, then atomizing being made powder packs into and is heated to 800 ℃, oxidation 10h in the high pressure vessel;
4, well-oxygenated powder is pressed into base substrate waiting under the static pressure 450MPa;
5, subsequently at 700 ℃ of sintering 10h of oxygen atmosphere;
6, with the base substrate behind the sintering at 800 ℃, hot pressing under the 400MPa pressure;
7, then with the hot pressing base substrate at 700 ℃ of resintering 10h of oxygen atmosphere;
8, base substrate behind the resintering is carried out hot extrusion and obtain the silk material, 850 ℃ of extrusion temperatures, mold preheating temperature are 450 ℃, and extrusion ratio is 400, extrusion speed 5cm/min.
The material property that present embodiment obtained is: tensile strength: 400MPa; Resistivity: 2.8 μ Ω .cm; Hardness: 120HV (annealed state); Density: 9.3g/cm
3The oxide particle mean particle size is 10 μ m.
Claims (10)
1. a silver oxide electrical contact material is characterized in that, component that comprises and weight percentage are: SnO
25～12%, ZnO 2～8%, and CuO 0.5～5%, 0.1～1%NiO, 0.1～0.5In
2O
3, 0.1～0.5%Bi
2O
3, surplus is Ag.
2, silver oxide electrical contact material as claimed in claim 1 is characterized in that, described SnO
2, ZnO, CuO, NiO, In
2O
3, Bi
2O
3Average particle size is between 0.1～10 μ m.
3. the preparation method of a silver oxide electrical contact material as claimed in claim 1 is characterized in that, may further comprise the steps:
The first step places the smelting furnace melting in proportion with silver ingot and Sn, Cu, Ni, Zn, Bi, In;
In second step, molten metal after the melting is carried out powder by atomization;
In the 3rd step, the powder that obtains atomizing is through preoxidation;
In the 4th step, powder isostatic pressing after the oxidation is become base substrate;
In the 5th step, will wait static pressure to obtain base substrate sintering under oxygen atmosphere;
In the 6th step, base substrate behind the sintering is carried out hot pressing;
In the 7th step, base substrate after the hot pressing is carried out resintering;
In the 8th step, base substrate behind the resintering is carried out hot extrusion obtain wire rod or band.
4. the preparation method of silver oxide electrical contact material as claimed in claim 3 is characterized in that, in the first step, and described melting, smelting temperature is between 950～1300 ℃.
5. the preparation method of silver oxide electrical contact material as claimed in claim 3 is characterized in that, in the 3rd step, and described preoxidation, wherein gaseous tension is between 0.1～3MPa, and temperature is between 450 ℃～850 ℃, and oxidization time is between 1h～10h.
6. the preparation method of silver oxide electrical contact material as claimed in claim 3 is characterized in that, in the 4th step, the described static pressure pressure that waits is between 100～500MPa.
7. the preparation method of silver oxide electrical contact material as claimed in claim 3 is characterized in that, in the 5th step, described sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
8. the preparation method of silver oxide electrical contact material as claimed in claim 3 is characterized in that, in the 6th step, described hot pressing temperature is 400～900 ℃, and hot pressing pressure is 300～700MPa, and hot pressing time is 1min～30min.
9. the preparation method of silver oxide electrical contact material as claimed in claim 3 is characterized in that, in the 7th step, described resintering technology is with the 4th step, and promptly sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
10. the preparation method of silver oxide electrical contact material as claimed in claim 3, it is characterized in that, in the 8th step, described base substrate behind the resintering is carried out hot extrusion, wherein the base substrate Heating temperature is at 600～900 ℃, extrusion ratio is between 10～400, and extrusion speed is 5～8cm/min, 100～500 ℃ of extrusion mould preheating temperatures.
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| CN116504550B (en) * | 2023-05-26 | 2023-10-24 | 江苏爱斯凯电气有限公司 | Electric contact material and preparation method thereof |
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