CN103695682B - A kind of silver oxide contact material and preparation method and products thereof with strengthening substrate performance additive - Google Patents

A kind of silver oxide contact material and preparation method and products thereof with strengthening substrate performance additive Download PDF

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Publication number
CN103695682B
CN103695682B CN201310700969.5A CN201310700969A CN103695682B CN 103695682 B CN103695682 B CN 103695682B CN 201310700969 A CN201310700969 A CN 201310700969A CN 103695682 B CN103695682 B CN 103695682B
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powder
oxide
additive
silver
substrate performance
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CN103695682A (en
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刘立强
颜小芳
鲁香粉
翁桅
柏小平
林万焕
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Zhejiang Fuda Alloy Materials Technology Co Ltd
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Fuda Alloy Materials Co Ltd
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Priority to PCT/CN2014/072141 priority patent/WO2015089940A1/en
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    • 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
    • C22C32/0015—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 with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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

Abstract

The invention discloses a kind of with silver oxide contact material preparation method strengthening substrate performance additive and products thereof, it is to be with additive alloy, oxidate powder, other additive powder and the silver ingot of strengthening the property for raw material, through water atomization pulverization, mixed powder, briquetting, sintering, extruding, finally carry out drawing or rolling, be prepared into contact material finished product.This invention has good electrical property and mechanical property silver matrix, and oxide particle and other additive homogenize material are dispersed in silver matrix, ensure that the features such as contact material electrical property is uniform and stable, and processing characteristics is good.The relatively traditional silver oxide contact material of the material prepared of this invented technology has higher anti-scorching, anti-electrotransfer, resistance fusion welding energy, can meet the requirement of the miniaturization of low-voltage apparatus volume, superior performance; This invented technology is simple, is applicable to batch production.The silver oxide product of preparation can be widely used in rly., contactor and isolating switch.

Description

A kind of silver oxide contact material and preparation method and products thereof with strengthening substrate performance additive
Technical field
The present invention relates to a kind of contact material and preparation method, especially a kind of silver oxide contact material and preparation method and products thereof with strengthening substrate performance additive.
Background technology
Silver oxide contact material to be applied in low-voltage apparatus the most extensive, especially in the contactor of big current grade, rly..Conventional silver oxide contact material is that " pseudoalloy " mode of simple silver and oxide compound exists, and oxide compound is dispersed in around fine silver matrix.The preparation method of comparatively common silver oxide contact material is internal oxidation process, blending processes of powders, powder pre-oxidation process and cladding process etc.These techniques all adopt adds oxide compound mode to improve the Wet Out between silver matrix and stannic oxide, as following patent:
CN201210335376.9 Composite silver stannic oxide electric contact material and manufacture method thereof, cardinal principle prepares stannic oxide and the dispersed mixture adding oxide compound, more fully mix with silver-colored solution, prepares composite silver stannic oxide materials.
The preparation method of a CN201210439786.8 siller tin oxide, cardinal principle adds oxidizing atmosphere in silver-colored stannum alloy powder atomization process, realizes the oxidation of powder.
The preparation method of CN201110331046.8 silver-stannic oxide by using physical metallurgical coating method, cardinal principle is at granules of stannic oxide Surface coating one deck alloy layer by physical metallurgy method, then become to add the coated granules of stannic oxide of oxide compound in oxidation conversion, mix with silver powder again, thus obtain silver tin oxide material.
This type of patent is all silver is above body material, improve electrical property by adding additive or improve oxide particle dispersiveness raising electrical property, these patents or technology all cannot improve the electrical property of silver matrix, and in the working process of contact, loaded current and arcing maximum be silver matrix.Because silver matrix performance does not have larger lifting, thus greatly limit the high current impulse withstanding capability of contact material, anti-DC condition under material transfer performance and the performance etc. of anti-contact melted.
At China, along with the raising day by day of people's living standard, various electrical equipment also gets more and more, and electrical equipment is also to miniaturization.This just requires that low-voltage apparatus needs to adapt to more loadtype, adapts to higher current class etc., and this just requires that contact material can meet higher rush of current performance, larger electric arc supporting capacity and less welding tendency.Conventional silver oxide contact material, under the prerequisite not solving silver matrix performance, just relies on the change of type or the change of composition of oxide compound, is difficult to meet the demands.
Summary of the invention
The object of the invention is the shortcoming and defect existed to overcome prior art, and a kind of preparation method of silver oxide contact material with strengthening substrate performance additive is provided, by the method can provide the high current impulse withstanding capability of matrix, anti-DC condition under material transfer performance and the performance of anti-contact melted.
For achieving the above object, technical scheme of the present invention is raw material is oxidate powder, strengthen substrate performance additive, the second additive powder, surplus is silver, second additive can be one or more combinations in Tungsten oxide 99.999, oxide compound molybdenum, rare earth oxide, Indium sesquioxide, nickel oxide, tellurium oxide, cupric oxide, bismuth oxide, strengthen substrate performance additive be bismuth, copper, indium, rare earth element, magnesium and zinc etc. any one or several arbitrarily, it is characterized in that making step is as follows successively:
(1) water atomization pulverization
By silver with strengthen substrate performance additive alloy through melting, water atomization, be prepared into the silver powder with increasing substrate performance
(2) mixed powder
Powder mix is prepared into by blending processes of powders by with the silver powder and oxidate powder, the second additive powder that strengthen substrate performance additive
(3) isostatic cool pressing
The powder mix of preparation is carried out isostatic cool pressing, is pressed into ingot;
(4) sinter
Ingot will be pressed into sinter;
(5) hot extrusion molding
By spindle heating also extrusion molding.
(6) forming materials processing
By the wire rod of extruding or Strip through drawing or be rolled into the finished product.
Further setting is that in described step (1), smelting temperature is at 1100-1300 DEG C, and atomization temperature is at 1000-1200 DEG C, and atomized water is pressed in 20-60MPa; The content increasing the additive alloy of substrate performance is 0.01-1% scope relative to silver-colored mass ratio; Increase substrate performance additive be bismuth, copper, indium, rare earth element, magnesium, nickel and zinc etc. any one or several arbitrarily, when containing multiple element, total content is no more than 1%.
Further setting mixes in powder in described step (2): the ratio of silver powder and oxide compound that band strengthens substrate performance additive is between 92:8 to 78:28; Additive powder ratio accounts for gross weight than being 0.01-6%; Silver powder granularity is-200 orders, and oxide compound degree is < 15 μm, and additive Powder Particle Size is < 30 μm; Blending processes of powders is any blending processes of powders such as dry-type mechanical mixes powder, wet type powder mixing machine, ball milling mixes powder, high-energy ball milling mixes powder.
Further setting is that the pressure of isostatic cool pressing in described step (3) is at 100MPa-250Mpa.
Further setting is described step (4) sintering, and wherein sintering temperature is 750 DEG C-920 DEG C, and the time is 2h-5h, under condition of nitrogen gas or under vacuum condition or under argon gas condition.
Further setting is the Heating temperature of described step (5) is 700 DEG C-900 DEG C, and extrusion speed, at 1-15mm/s, is wire rod or band or sheet material after extrusion molding.
Another object of the present invention provides a kind of silver oxide contact material with strengthening substrate performance additive, its technical scheme comprises following component: oxidate powder, strengthen substrate performance additive, the second additive powder, surplus is silver, second additive can be Tungsten oxide 99.999, oxide compound molybdenum, rare earth oxide, Indium sesquioxide, nickel oxide, tellurium oxide, cupric oxide, bismuth oxide, strengthen substrate performance additive be bismuth, copper, indium, rare earth element, magnesium, nickel and zinc etc. any one or several arbitrarily.
The maximum feature of the present invention adopts the silver powder with the additive strengthening substrate performance, thus to solve silver matrix in conventional silver oxide material be fine silver matrix, and its anti-current impact, arc erosion, resistance fusion welding can be all poor; Improve Wet Out between silver and oxide compound simultaneously, oxide material is enclosed in all the time with in the silver matrix of strengthening the property, reduces the gathering of oxide compound, floating trend, further increase the anti-electric-arc ablation ability of contact material; Simultaneously owing to increasing the lower of the additive alloy overall control of substrate performance, substantially can not reduce the conductivity of silver matrix, even can improve its conductivity further, so this material performance also can ensure.The silver powder water atomization technology of preparing of the additive with enhancing substrate performance that the present invention adopts, contact material mix powder technology of preparing, and equal technique is very simple, is applicable to industrialized mass.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Fig. 1 present invention process schema.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
embodiment 1
With AgLa-SnO 210 materials are prepared as example
1,19.98kgAg ingot, 0.02kgMg melting under 1300 DEG C of conditions, then at 1250 DEG C of Water Under powder by atomizations, water atomization pressure is 38MPa, and last powder crosses 200 mesh sieves, thus obtains AgLa alloy powder;
2, the SnO of the AgLa powder of 9kg and 3 μm of 1kg 2powder machinery is dry mixed powder and prepares AgLa-SnO 210 powder;
3, AgLa-SnO 210 powder ingot processed under 180MPa pressure on cold isostatic press, spindle diameter 85mm.
4, AgLa-SnO 210 spindles sinter 4h under vacuum, sintering temperature 850 DEG C.
5, AgLa-SnO 210 spindles extrude under 800 DEG C of conditions, and extruding specification is Φ 6.
6, AgLa-SnO 210 wire rods are through cold drawing machine, and cold drawing is to the diameter dimension needed.
AgLa-SnO prepared by this example 210 physicalies are as follows: density 10.1g/cm 3, resistivity 2.2 μ Ω .cm, hardness (HV0.3) 91(half-hard state), tensile strength 331MPa.
embodiment 2
With AgMgNi-SnO 2in 2o 312 materials are prepared as example
1, the Ag ingot of 19.98kg, the Ni sheet of 0.01kg, the melting under 1200 DEG C of conditions of 0.01kgMg ingot, then at 1150 Water Under powder by atomizations, water atomization pressure is 42MPa, and last powder crosses 200 mesh sieves, thus obtains AgMgNi alloy powder;
2, the SnO of the AgMgNi powder of 8.8kg and 4 μm of 1.0kg 2the In of 5 μm of powder, 0.2kg 2o 3powder machinery is dry mixed powder and prepares AgMgNi-SnO 2in 2o 312 powder;
3, AgMgNi-SnO 2in 2o 312 powder ingot processed under 220MPa pressure on cold isostatic press, spindle diameter 86mm.
4, AgMgNi-SnO 2in 2o 312 spindles sinter 4h under vacuo, sintering temperature 860 DEG C.
5, AgMgNi-SnO 2in 2o 312 spindles extrude under 820 DEG C of conditions, and extruding specification is Φ 6.
6, AgMgNi-SnO 2in 2o 312 wire rods are through cold drawing machine, and cold drawing is to the diameter dimension needed.
AgMgNi-SnO prepared by this example 2in 2o 312 material contact physicalies are as follows: density 9.91g/cm 3, resistivity 2.38 μ Ω .cm, hardness (HV0.3) 102, tensile strength 354MPa.
embodiment 3
Example is prepared as with AgCuNi-ZnO10 material
1, Ag ingot, the Cu rod of 0.01kg, the Ni sheet of 0.01kg of 19.98kg, melting under 1300 DEG C of conditions, then at 1250 DEG C of Water Under powder by atomizations, water atomization pressure is 60MPa, and last powder crosses 200 mesh sieves, thus obtains AgCuNi alloy powder;
2, the ZnO powder machinery of the AgCuNi powder of 9kg and 7 μm of 1kg is dry mixed powder and prepares AgCuNi-ZnO10 powder;
3, AgCuNi-ZnO10 powder ingot processed under 180MPa pressure on cold isostatic press, spindle diameter 83mm.
4, AgCuNi-ZnO10 spindle sinters 4h under vacuum, sintering temperature 800 DEG C.
5, AgCuNi-ZnO10 spindle extrudes under 780 DEG C of conditions, and extruding specification is 40X4.
6, AgCuNi-ZnO10 band through cold rolling mill, punching to need specification.
AgCuNi-ZnO10 sheet point physicals prepared by this example is as follows: density 9.68g/cm 3, resistivity 2.29 μ Ω .cm, hardness (HV0.3) 87.

Claims (5)

1. the silver oxide contact material preparation method with strengthening substrate performance additive, it is characterized in that: raw material is oxidate powder, strengthen substrate performance additive, the second additive powder, surplus is silver, second additive can be any one or any several combination in Tungsten oxide 99.999, molybdenum oxide, rare earth oxide, Indium sesquioxide, nickel oxide, tellurium oxide, cupric oxide, bismuth oxide, strengthen substrate performance additive be in bismuth, copper, indium, rare earth element, magnesium and zinc any one or several arbitrarily, making step is as follows successively:
(1) water atomization pulverization
By silver with strengthen substrate performance additive alloy through melting, water atomization, be prepared into the silver powder with increasing substrate performance
(2) mixed powder
Powder mix is prepared into by blending processes of powders by with the silver powder and oxidate powder, the second additive powder that strengthen substrate performance additive
(3) isostatic cool pressing
The powder mix of preparation is carried out isostatic cool pressing, is pressed into ingot;
(4) sinter
Ingot will be pressed into sinter;
(5) hot extrusion molding
By spindle heating also extrusion molding;
(6) forming materials processing
By the wire rod of extruding or Strip through drawing or be rolled into the finished product.
In described step (1), smelting temperature is at 1100-1300 DEG C, and atomization temperature is at 1000-1200 DEG C, and atomized water is pressed in 20-60MPa; The content increasing the additive alloy of substrate performance is 0.01-1% scope relative to silver-colored mass ratio; Increase substrate performance additive be in bismuth, copper, indium, rare earth element, magnesium, nickel and zinc any one or several arbitrarily, when containing multiple element, total content is no more than 1%,
In described step (2) in mixed powder: the ratio of silver powder and oxide compound that band strengthens substrate performance additive is between 92:8 to 78:28; Additive powder ratio accounts for gross weight than being 0.01-6%; Silver powder granularity is-200 orders, and oxide compound degree is < 15 μm, and additive Powder Particle Size is < 30 μm; Blending processes of powders is that dry-type mechanical mixes powder, wet type powder mixing machine or ball milling and mixes powder.
2. a kind of silver oxide contact material preparation method with strengthening substrate performance additive according to claim 1, is characterized in that: in described step (3), the pressure of isostatic cool pressing is at 100MPa-250Mpa.
3. a kind of silver oxide contact material preparation method with strengthening substrate performance additive according to claim 1, it is characterized in that: described step (4) sinters, wherein sintering temperature is 750 DEG C-920 DEG C, time is 2h-5h, under condition of nitrogen gas or under vacuum condition or under argon gas condition.
4. a kind of silver oxide contact material preparation method with strengthening substrate performance additive according to claim 1, it is characterized in that: the Heating temperature of described step (5) is 700 DEG C-900 DEG C, extrusion speed, at 1-15mm/s, is wire rod or band or sheet material after extrusion molding.
5. the band that prepared by a preparation method as claimed in claim 1 strengthens the silver oxide contact material of substrate performance additive, it is characterized in that comprising following component: oxidate powder, strengthen substrate performance additive, second additive powder, surplus is silver, second additive can be Tungsten oxide 99.999, molybdenum oxide, rare earth oxide, Indium sesquioxide, nickel oxide, tellurium oxide, cupric oxide, in bismuth oxide any one or several arbitrarily, strengthening substrate performance additive is bismuth, copper, indium, rare earth element, magnesium, in nickel and zinc any one or several arbitrarily, the mass ratio of silver powder and oxide compound that band strengthens substrate performance additive is between 92:8 to 78:28, second additive powder ratio accounts for gross weight than being 0.01-6%, strengthen the 0.01-1% that substrate performance additive accounts for total content.
CN201310700969.5A 2013-12-18 2013-12-18 A kind of silver oxide contact material and preparation method and products thereof with strengthening substrate performance additive Active CN103695682B (en)

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PCT/CN2014/072141 WO2015089940A1 (en) 2013-12-18 2014-02-17 Sliver oxide contact material with matrix performance-enhancing additive as well as preparation method and product thereof

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CN108015276B (en) * 2017-11-29 2019-08-23 温州宏丰电工合金股份有限公司 A kind of reinforced phase gradient distribution infiltration class silver-based electric contact material and preparation method thereof
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