CN101651051A - Cadmium-oxygen-silver multicomponent electrical contact material and preparation method thereof - Google Patents
Cadmium-oxygen-silver multicomponent electrical contact material and preparation method thereof Download PDFInfo
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- CN101651051A CN101651051A CN200910055062A CN200910055062A CN101651051A CN 101651051 A CN101651051 A CN 101651051A CN 200910055062 A CN200910055062 A CN 200910055062A CN 200910055062 A CN200910055062 A CN 200910055062A CN 101651051 A CN101651051 A CN 101651051A
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Abstract
The invention discloses a cadmium-oxygen-silver multicomponent electrical contact material and a preparation method thereof. The material comprises the following components by weight percent: one of 5-12% of CdO, 1-5% of ZnO or 1-5% of SnO2 and the balance Ag. The invention adopts multicomponent reinforcement in the raw material and combines the advantages of all the reinforced phases so as to ensure that the material not only maintains the advantages of Ag-CdO such as good fusion welding resistance, strong breaking ability, low temperature rise and the like, but also has lower dosage of toxiccadmium, better electric arc burning loss resistance property and obvious silver-saving effect, and can replace cadmium-oxygen-silver to be used in the high power relay so as to reduce the environmental pollution caused by the production and application processes of the cadmium-oxygen-silver contact.
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 cadmium-oxygen-silver multicomponent electrical contact material and preparation method thereof.
Background technology
Along with the direction of electric equipment products to big capacity, small size develops, the requirement of electric contact material is increased day by day---require material under the condition of greatly arc heat and Joule heat, melting welding, machinery and anti-electric abrasioning performance not to take place will to get well; The metal that produces in breaking course splashes few, and the arcing time is short; 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 in the product, later on can residual cadmium salt in environment.Because it is cadmium metal and cadmium salt have very big toxic and side effect to human body, harmful to environment.
Therefore seek and to substitute the focus that the novel electric contact material of Ag-CdO becomes present domestic and international research fully.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) oxide based electric contact material of Ag-and the relay, alternating current general-purpose relay, the automobile relay CN101208762A that use this material
(2) manufacture method of silver-oxide based contact material and goods CN1571856A thereof
(3) siller tin oxide cupric oxide alloy contact material C N1441071A
(4) silver-tin oxide or indium oxide electric contact wire rod and production technology CN1167835A thereof
(5) method of preparing novel silver tin oxide silk electrical contact material CN101202169A
(6) siller tin oxide zinc oxide alloy electric contact and production technology CN1443864A thereof
In sum, mainly concentrate on AgSnO about the research that substitutes the AgCdO material both at home and abroad now
2, the AgZnO material design of components and preparation method, develop the AgSnO of a plurality of series
2Or the no cadmium composite material of Ag-ZnO.These materials are because SnO
2Or ZnO particle thermal stability is better, so in use the loss of material is less, has good joint silver effect.Problems such as but temperature rise is too high in following process difficulty, the use, breaking capacity is more weak still are not well solved, to such an extent as to still can not substitute the Ag-CdO material in a lot of high-power applications occasions.
Summary of the invention
The present invention is directed to the above deficiency that prior art exists, a kind of Agcdo base multicomponent electrical contact material and preparation method thereof is provided, polynary reinforced composite based on the CdO particle, make it on the basis of advantages such as keeping Ag-CdO material behavior-strong, resistance fusion welding good, temperature rise is lower as breaking capacity, reduce the Cd consumption, reduce material loss in use, have excellent comprehensive performances, easy to process.
For realizing above-mentioned purpose, the technical solution used in the present invention is:
The invention provides a kind of Agcdo base multicomponent electrical contact material, component that it comprises and weight percentage are: CdO 5～12%, and ZnO 1～5%, SnO
2At least a in 1～5%, surplus is Ag.
The above-mentioned electric contact material of the present invention can further include at least three kinds in the following trace mineral supplement: CuO 0.1～2%, 0.1～1%NiO, 0.1～0.5%In
2O
3, 0.1～0.5%Bi
2O
3, be weight percent content.
Described CdO, ZnO, SnO
2, CuO, NiO, In
2O
3, Bi
2O
3Average particle size is between 0.3～10 μ m.
The present invention also provides the preparation method of above-mentioned Agcdo base multicomponent electrical contact material, may further comprise the steps:
The first step places the smelting furnace melting in proportion with silver ingot and required alloying element metal derby;
Described smelting temperature is between 950-1300 ℃.
Described alloying element is meant and comprises at least a in Cd metallic element and Zn, the Sn metal.
Described alloying element can also comprise at least three kinds in Cu, Ni, In, the Bi metal.
In second step, the molten metal that the first step is obtained carries out powder by atomization;
Described powder by atomization is meant and utilizes gases at high pressure or water impact fused solution metal flow, makes it be atomized into the metal droplet, and cooling subsequently obtains powder.
Described powder by atomization, wherein atomization pressure is between 0.3MPa～10MPa.
Second step is with the powder oxidation of atomizing acquisition;
Described oxidation, wherein gas pressure is between 0.1～3MPa, and temperature is between 500 ℃～850 ℃, and oxidization time is between 1h～10h;
In the 3rd step, powder isostatic pressing after the oxidation is become base substrate;
The described static pressure pressure that waits is between 100～500MPa.
In the 4th 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 5th step, base substrate behind the sintering is carried out hot pressing;
Described hot pressing, wherein hot pressing temperature is 400～900 ℃, hot pressing pressure is 300～700MPa.
The 6th step, base substrate after the hot pressing is carried out resintering, resintering technology is with the 4th step;
Described resintering, wherein sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
In the 7th step, base substrate behind the resintering is carried out hot extrusion obtain wire rod or band.
Described base substrate heating-up temperature is at 600～900 ℃, and extrusion ratio is between 10～400, and extrusion speed is 5～8cm/min, 100～500 ℃ of extrusion die preheat temperatures.
It is main wild phase that the present invention adopts with the cadmium oxide particle, mixes other necessity as ZnO, SnO
2Strengthen Deng granulated multicomponent.Such material design has not only kept the characteristics that cadmium oxide material breaking capacity is strong, resistance fusion welding is good, and can bring into play ZnO, SnO
2The advantage that particle arc ablation resistance ability is strong, such design philosophy has not only reduced the pollution of poisonous cadmium element, and can further improve the performance of material.Add simultaneously such as elements such as Cu, Ni, In, Bi, make Zn element and Sn element realize preoxidation process easily, shorten oxidization time, can strengthen the wetability of oxide particle and matrix simultaneously, make material temperature rise in use reach instructions for use, and increase the service life.
Compare with sheet material with existing electric contact, the present invention is owing to added the element components of above necessity in raw material, the preparation method who has adopted powder metallurgy to combine with hot extrusion deformation, thereby reach good processing properties, poisonous cadmium content reduces, and can replace Agcdo to be applied to high power relay.Material of the present invention has reduced the pollution of production application process in Agcdo contact to environment, and has the silver-colored effect of better joint.
Description of drawings
Fig. 1 is the flow chart of material preparation method of the present 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
In the present embodiment, component that cadmium-oxygen-silver multicomponent electrical contact material comprises and weight percentage are: 5%CdO, 5%SnO
2, 1%CuO, 0.5%NiO, 0.5%In
2O
3, surplus is Ag
Take by weighing the 17.8Kg silver ingot, place intermediate frequency furnace to melt, add 1Kg Cd, 0.8Kg Sn, 0.2kg Cu, 0.1kg Ni, 0.1kg In subsequently successively, after 950 ℃ of melting homogenizing, powder by atomization under the 10MPa nitrogen pressure, then atomizing is made powder and pack into and be heated to 500 ℃ in the high-pressure bottle, oxidation 10h, oxygen pressure are 3MPa.Well-oxygenated powder is pressed into base substrate waiting under the static pressure 100MPa, subsequently at 600 ℃ of sintering 10h of oxygen atmosphere.With the base substrate behind the sintering at 900 ℃, hot pressing under the 300MPa pressure, then with the hot pressing base substrate at 850 ℃ of resintering 5h of oxygen atmosphere.Base substrate behind the resintering is carried out hot extrusion, and 600 ℃ of extrusion temperatures, mold preheating temperature are 100 ℃, and extrusion ratio is 10, extrusion speed 5cm/min.The material property that is obtained is: tensile strength: 315MPa; Resistivity: 2.2 μ Ω .cm; Hardness: 95HV (annealed state); Density: 10.0g/cm
3The oxide particle particle mean size is 0.3 μ m.
Embodiment two
In the present embodiment, component that cadmium-oxygen-silver multicomponent electrical contact material comprises and weight percentage are: 6%CdO, 2%ZnO, 0.3%Bi
2O
3, 0.1%NiO, 0.5%In
2O
3, surplus is Ag
Take by weighing the 18Kg silver ingot, place intermediate frequency furnace to melt, add 1.2Kg Cd, 0.4Kg Zn, 0.3kg Cu, 0.02kg Ni, 0.06kg Bi, 0.1kg In subsequently successively, after 1300 ℃ of melting homogenizing, under the 0.3MPa nitrogen pressure, powder by atomization makes atomizing powder then and packs into and be heated to 850 ℃ in the high-pressure bottle, oxidation 1h, oxygen pressure are 0.1MPa.Well-oxygenated powder is pressed into base substrate waiting under the static pressure 500MPa, subsequently at 900 ℃ of sintering 2h of oxygen atmosphere.With the base substrate behind the sintering at 400 ℃, hot pressing under the 700MPa pressure, then with the hot pressing base substrate at 900 ℃ of resintering 2h of oxygen atmosphere.Base substrate behind the resintering is carried out hot extrusion, and 900 ℃ of extrusion temperatures, mold preheating temperature are 500 ℃, and extrusion ratio is 400, extrusion speed 8cm/min.The material property that is obtained is: tensile strength: 280MPa; Resistivity: 2.0 μ Ω .cm; Hardness: 75HV (annealed state); Density: 10.1g/cm
3The oxide particle particle mean size is 0.5 μ m
Embodiment three
In the present embodiment, component that cadmium-oxygen-silver multicomponent electrical contact material comprises and weight percentage are: 7%CdO, 6%SnO
2, 0.1%CuO, 0.5%NiO, 0.5%Bi
2O
3, surplus is Ag
Take by weighing the 17Kg silver ingot, place intermediate frequency furnace to melt, add 1.4KgCd, 1.2KgZn, 0.02kgCu, 0.1kgNi, 0.1kgBi subsequently successively, after 1150 ℃ of melting homogenizing, under the 5MPa nitrogen pressure, powder by atomization makes atomizing powder then and packs into and be heated to 650 ℃ in the high-pressure bottle, oxidation 8h, oxygen pressure are 1MPa.Well-oxygenated powder is pressed into base substrate waiting under the static pressure 250MPa, subsequently at 750 ℃ of sintering 5h of oxygen atmosphere.With the base substrate behind the sintering at 750 ℃, hot pressing under the 500MPa pressure, then with the hot pressing base substrate at 750 ℃ of resintering 5h of oxygen atmosphere.Base substrate behind the resintering is carried out hot extrusion, and mold preheating temperature is 350 ℃, 700 ℃ of extrusion temperatures, and extrusion ratio is 250, extrusion speed 7cm/min.The material property that is obtained is: tensile strength: 330MPa; Resistivity: 2.3 μ Ω .cm; Hardness: 90HV (annealed state); Density: 9.85g/cm
3The oxide particle particle mean size is 1 μ m.
Embodiment four
In the present embodiment, component that cadmium-oxygen-silver multicomponent electrical contact material comprises and weight percentage are: 10%CdO, 3%ZnO, 2%CuO, 0.2%NiO, 0.3%In
2O
3, 0.5Bi
2O
3, surplus is Ag
Take by weighing the 16.8Kg silver ingot, place intermediate frequency furnace to melt, add 2.0KgCd, 0.6KgZn, 0.4kgCu, 0.04kgNi, 0.1kgBi, 0.06kgIn subsequently successively, after homogenizing, under the 2MPa nitrogen pressure, 1050 ℃ of powder by atomizations make atomizing powder then and pack into and be heated to 700 ℃, oxidation 8h in the high-pressure bottle.Well-oxygenated powder is pressed into base substrate waiting under the static pressure 300MPa, subsequently at 850 ℃ of sintering 5h of oxygen atmosphere.With the base substrate behind the sintering at 750 ℃, hot pressing under the 550MPa pressure, then with the hot pressing base substrate at 850 ℃ of resintering 5h of oxygen atmosphere.Base substrate behind the resintering is carried out hot extrusion obtain the silk material, 700 ℃ of extrusion temperatures, mold preheating temperature are 400 ℃, and extrusion ratio is 200, extrusion speed 6cm/min.The material property that is obtained is: tensile strength: 350MPa; Resistivity: 2.4 μ Ω .cm; Hardness: 100HV (annealed state); Density: 9.7g/cm
3The oxide particle particle mean size is 2 μ m.
Embodiment five
In the present embodiment, component that cadmium-oxygen-silver multicomponent electrical contact material comprises and weight percentage are: 12%CdO, 1%ZnO, 1%SnO
2, 0.1%NiO, 0.1In
2O
3, 0.2Bi
2O
3, surplus is Ag
Take by weighing the 17.6Kg silver ingot, place intermediate frequency furnace to melt, add 2.4Kg Cd, 0.16KgZn, 0.2kgSn, 0.02kgNi, 0.04kgBi, 0.02kgIn subsequently successively, after homogenizing, under the 1MPa nitrogen pressure, 1250 ℃ of powder by atomizations make atomizing powder then and pack into and be heated to 800 ℃, oxidation 3h in the high-pressure bottle.Well-oxygenated powder is pressed into base substrate waiting under the static pressure 300MPa, subsequently at 850 ℃ of sintering 5h of oxygen atmosphere.With the base substrate behind the sintering at 750 ℃, under the 400MPa pressure hot pressing then with the hot pressing base substrate at 850 ℃ of resintering 5h of oxygen atmosphere.Base substrate behind the resintering is carried out hot extrusion 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 is obtained is: tensile strength: 340MPa; Resistivity: 2.3 μ Ω .cm; Hardness: 105HV (annealed state); Density: 9.8g/cm
3The oxide particle particle mean size is 2 μ m.
Implement six
In the present embodiment, component that cadmium-oxygen-silver multicomponent electrical contact material comprises and weight percentage are: 5%CdO, 5%ZnO, 5%SnO
2, 0.2%NiO, 0.5%In
2O
3, 0.3%Bi
2O
3, surplus Ag
Take by weighing the 16.8Kg silver ingot, place intermediate frequency furnace to melt, add 1.8KgCd, 0.4KgZn, 0.8kg Cu, 0.04kg Ni, 0.06kg Bi, 0.1kg In subsequently successively, after homogenizing, under the 3MPa nitrogen pressure, 1100 ℃ of powder by atomizations make atomizing powder then and pack into and be heated to 800 ℃, oxidation 10h in the high-pressure bottle.Well-oxygenated powder is pressed into base substrate waiting under the static pressure 450MPa, subsequently at 700 ℃ of sintering 10h of oxygen atmosphere.With the base substrate behind the sintering at 800 ℃, hot pressing under the 400MPa pressure, then with the hot pressing base substrate at 700 ℃ of resintering 10h of oxygen atmosphere.Base substrate behind the resintering is carried out hot extrusion 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 is obtained is: tensile strength: 380MPa; Resistivity: 2.45 μ Ω .cm; Hardness: 100HV (annealed state); Density: 9.78g/cm
3The oxide particle particle mean size is 3 μ m.
Claims (14)
1, a kind of cadmium-oxygen-silver multicomponent electrical contact material, it is characterized in that the component and the weight percentage that comprise are: CdO 5～12%, and ZnO 1～5%, SnO
2At least a in 1～5%, surplus is Ag.
2. cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 1 is characterized in that, further comprises at least three kinds in the following trace mineral supplement: CuO 0.1～2%, 0.1～1%NiO, 0.1～0.5In
2O
3, 0.1～0.5%Bi
2O
3, be weight percentage herein.
3. cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 2 is characterized in that, described CuO, NiO, In
2O
3, Bi
2O
3Average particle size is between 0.3～10 μ m.
4. cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 1 is characterized in that, described CdO, ZnO, SnO
2Average particle size is between 0.3～10 μ m.
5. the preparation method of a cadmium-oxygen-silver multicomponent 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 required alloying element metal derby;
In second step, the molten metal that the first step is obtained carries out powder by atomization;
In the 3rd step, the powder that atomizing is obtained carries out oxidation;
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;
The 7th step, base substrate after the hot pressing is carried out resintering, resintering technology is with the 4th step;
In the 8th step, base substrate behind the resintering is carried out hot extrusion obtain wire rod or band.
6, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the first step, and described melting, wherein smelting temperature is between 950～1300 ℃.
7, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5, it is characterized in that, in the first step, described alloying element, be meant and comprise and at least a in Cd metallic element and Zn, the Sn metal can also comprise at least three kinds in Cu, Ni, In, the Bi metal.
8. the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in second step, and described atomizing, atomization pressure is between 0.3MPa～10MPa.
9, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the 3rd step, described oxidation, wherein gas pressure is between 0.1～3MPa, and temperature is between 350 ℃～850 ℃, and oxidization time is between 1h～10h.
10, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the 4th step, the described static pressure pressure that waits is between 100～500MPa.
11, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the 5th step, described sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
12, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the 6th step, and described hot pressing, wherein hot pressing temperature is 400～900 ℃, and hot pressing pressure is 300～700MPa, and hot pressing time is 1min～30min.
13, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the 7th step, and described resintering, wherein sintering temperature is at 600～900 ℃, and sintering time is between 2h～10h.
14, the preparation method of cadmium-oxygen-silver multicomponent electrical contact material as claimed in claim 5 is characterized in that, in the 8th step, described base substrate heating-up temperature is at 600～900 ℃, extrusion ratio is between 10～400, and extrusion speed is 5～8cm/min, 100～500 ℃ of extrusion die preheat temperatures.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031408A (en) * | 2010-12-30 | 2011-04-27 | 温州宏丰电工合金股份有限公司 | Method for preparing silver-based oxide electrical contact material with fibrous structure |
| CN102074386A (en) * | 2011-02-18 | 2011-05-25 | 司捷易兰姆布斯控制科技（苏州）有限公司 | Electric contact for touch switch |
| CN102319901A (en) * | 2011-10-20 | 2012-01-18 | 福达合金材料股份有限公司 | Preparation method for silver cadmium oxide electrical contact |
| CN104131246A (en) * | 2014-07-02 | 2014-11-05 | 昆明理工大学 | Nickel-fiber-containing silver metal-oxide electrical contact material and preparation method thereof |
| CN105702503A (en) * | 2016-04-11 | 2016-06-22 | 福达合金材料股份有限公司 | Preparation method for silver tin oxide indium oxide contact material |
| 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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2009
- 2009-07-20 CN CN2009100550621A patent/CN101651051B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031408A (en) * | 2010-12-30 | 2011-04-27 | 温州宏丰电工合金股份有限公司 | Method for preparing silver-based oxide electrical contact material with fibrous structure |
| CN102031408B (en) * | 2010-12-30 | 2012-08-22 | 温州宏丰电工合金股份有限公司 | Method for preparing silver-based oxide electrical contact material with fibrous structure |
| CN102074386A (en) * | 2011-02-18 | 2011-05-25 | 司捷易兰姆布斯控制科技（苏州）有限公司 | Electric contact for touch switch |
| CN102319901A (en) * | 2011-10-20 | 2012-01-18 | 福达合金材料股份有限公司 | Preparation method for silver cadmium oxide electrical contact |
| CN104131246A (en) * | 2014-07-02 | 2014-11-05 | 昆明理工大学 | Nickel-fiber-containing silver metal-oxide electrical contact material and preparation method thereof |
| CN105702503A (en) * | 2016-04-11 | 2016-06-22 | 福达合金材料股份有限公司 | Preparation method for silver tin oxide indium oxide contact material |
| 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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