CN116926363A - Silver-molybdenum-tungsten electric contact material and preparation method thereof - Google Patents
Silver-molybdenum-tungsten electric contact material and preparation method thereof Download PDFInfo
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- CN116926363A CN116926363A CN202310812555.5A CN202310812555A CN116926363A CN 116926363 A CN116926363 A CN 116926363A CN 202310812555 A CN202310812555 A CN 202310812555A CN 116926363 A CN116926363 A CN 116926363A
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- silver
- molybdenum
- tungsten
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- HFXNGBXJALHADJ-UHFFFAOYSA-N [Mo].[W].[Ag] Chemical compound [Mo].[W].[Ag] HFXNGBXJALHADJ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011812 mixed powder Substances 0.000 claims abstract description 21
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 17
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001764 infiltration Methods 0.000 claims abstract description 13
- 230000008595 infiltration Effects 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QEKREONBSFPWTQ-UHFFFAOYSA-N disilver dioxido(dioxo)tungsten Chemical compound [Ag+].[Ag+].[O-][W]([O-])(=O)=O QEKREONBSFPWTQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 230000000754 repressing effect Effects 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 238000011049 filling Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000002829 reductive effect Effects 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- OMSFUHVZHUZHAW-UHFFFAOYSA-N [Ag].[Mo] Chemical compound [Ag].[Mo] OMSFUHVZHUZHAW-UHFFFAOYSA-N 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- UYKQQBUWKSHMIM-UHFFFAOYSA-N silver tungsten Chemical compound [Ag][W][W] UYKQQBUWKSHMIM-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000009740 moulding (composite fabrication) Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- ITZSSQVGDYUHQM-UHFFFAOYSA-N [Ag].[W] Chemical class [Ag].[W] ITZSSQVGDYUHQM-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000000626 liquid-phase infiltration Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
-
- 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
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a silver-molybdenum-tungsten electric contact material, which comprises the following steps: adding ammonia water, deionized water, oxalic acid and dilute nitric acid into the mixed powder of molybdenum oxide, tungsten oxide and silver nitrate to obtain precipitates such as silver molybdate, silver tungstate, molybdic acid, tungstic acid and the like; drying the obtained precipitate, and carrying out reduction treatment in reducing atmospheres at two different temperatures; mechanically crushing and spheroidizing the reduced powder, and sieving; sintering and granulating the sieved powder at high temperature in a reducing atmosphere; and (3) carrying out molding, sintering, infiltration and repressing treatment on the granulated mixed powder to obtain the silver-molybdenum-tungsten electrical contact material. The invention adopts the methods of precipitation and twice reduction to accurately control the components of the composite powder and manufacture the nano-grade composite powder, and the composite powder is mechanically crushed in the process, the particle shape is sphericized to improve the fluidity, the filling property and the like, and the manufacturing process is simple and is suitable for mass production.
Description
Technical Field
The invention relates to the field of electric contact materials, in particular to a silver-molybdenum-tungsten electric contact material and a preparation method thereof.
Background
Silver-molybdenum contact materials are widely applied in the field of circuit breakers, and on one hand, micron-sized molybdenum particles are contained in the materials as reinforcing phases, so that the arc ablation resistance of the contact materials can be greatly improved; on the other hand, the material is manufactured by adopting a powder metallurgy method and a liquid phase infiltration process, and can ensure that molybdenum particles and a silver matrix form good wetting, so that the material is reduced to splash under the action of high-temperature electric arcs, and the material has good arc erosion resistance.
In order to continue to improve the arc erosion resistance of the silver-molybdenum material, it is common practice to use finer molybdenum powder as the raw material while increasing the molybdenum content of the silver-molybdenum contact material. When the content of molybdenum in the silver-molybdenum powder is too high and the mass percentage of molybdenum particles is increased to 60% -85% when the content of molybdenum particles is too small, the dispersibility, the processability and the infiltration difficulty of the molybdenum particles are improved greatly, the agglomeration of the molybdenum particles and additive particles cannot be avoided by a conventional powder mixing process or a conventional coating process, and the inherent air holes in the preparation process of the coating powder cannot be removed, so that the aggregation phenomenon of the enhanced phase in the preparation of the silver-molybdenum contact material by the conventional powder mixing process cannot be completely eradicated; the coating process cannot avoid air holes, layering of products after infiltration, holes on the section, aggregation, exposed reinforcing phase particles, and poor combination of silver and molybdenum.
Silver tungsten composites are typically chemically clad and powder metallurgically processed. The chemical coating reaction is carried out in a liquid system, and because the density difference between the tungsten powder and the silver powder is too large, the tungsten powder sinks in the reaction liquid at a high speed, so that the phenomenon of serious agglomeration and aggregation exists, and the truly uniform composite powder is difficult to obtain. The mode of mixing the silver powder and the tungsten powder according to the proportion leads to the prolongation of the production period and the increase of the energy consumption on one hand due to the addition of the ball milling treatment procedure; on the other hand, impurities carried in during ball milling still have an adverse effect on the performance of the resulting contacts.
Tungsten molybdenum is two elements in the same column of the periodic table. They have similar characteristics and crystal structures, so that tungsten and molybdenum can be in solid solution in any proportion, and therefore, adding tungsten to silver-molybdenum alloy for solid solution is one of ways to optimize molybdenum structure and improve performance.
The molybdenum trioxide, the tungsten trioxide and the silver nitrate are mixed into the solution for precipitation, and as the three substances are easy to be dissolved in ammonia water, the problem of large density difference does not exist, and the precipitated product is a fixed product and has no impurity. Oxalic acid is added to accelerate nucleation rate, and then oxalic acid dissolved in water is separated out again and adsorbed by molybdic acid and tungstic acid colloidal particles, so that molybdic acid particles and tungstic acid particles are isolated from each other to avoid growth of molybdic acid particles and tungstic acid particles, and nano-scale powder can be obtained.
The invention patent with publication number CN102392170A discloses a processing method for manufacturing a silver-tungsten composite contact material, which comprises the following steps: after adding water and proper amount of reducer into a reaction vessel, slowly spraying silver ammonia complex solution under stirring, washing the silver-tungsten coated powder to neutral and drying, then performing uniform ball milling treatment by a high-energy ball mill, performing preliminary press forming after stress relief treatment on the silver-tungsten powder, and performing presintering, infiltration sintering and re-pressing under the protection of a reducing atmosphere to obtain the silver-tungsten composite contact material. Although the silver-tungsten contact material with high mortality is obtained by adopting a chemical coating method, the chemical coating reaction is required to be carried out in a liquid system, and because the density difference between tungsten powder and silver powder is too large, the tungsten powder sinks in a reaction liquid at a high speed, so that the phenomenon of serious agglomeration aggregation exists, and the truly uniform composite powder is difficult to obtain.
The invention patent of publication No. CN104480335A discloses a preparation method of a silver-tungsten contact material, which comprises the steps of mixing silver powder and tungsten powder, putting the obtained silver-tungsten mixed powder, high-purity nickel balls and water into a ball mill for ball milling, and drying, annealing, forming and infiltration treatment the obtained ball-milled silver-tungsten mixed powder to obtain the silver-tungsten contact material, wherein the ball milling medium is water, the high-purity nickel balls are worn by hard particle tungsten in the ball milling process to obtain micro-nano nickel powder, and at the moment, the high temperature generated in the ball milling process is enough to oxidize the micro-nano nickel powder in the water to generate nickel oxide, the nickel oxide cannot be combined with the tungsten, and then nickel-coated tungsten particles cannot be obtained. In addition, the improved element nickel is introduced by a grinding ball mode, the obtained nickel particles are of irregular morphology, the nickel content is extremely difficult to control, the requirements of the electric contact field cannot be met, and the large-scale production and application cannot be stably carried out
The invention patent of publication No. CN114182122A discloses a high-dispersity silver-molybdenum electrical contact material and a preparation method thereof, and the invention discloses a high-dispersity silver-molybdenum electrical contact material and a preparation method thereof, wherein additives can be effectively dispersed through ball milling pretreatment of coating early-stage molybdenum powder and additives, so that the additives uniformly grow on the surface of molybdenum powder, the effect of the additives is exerted to the greatest extent, then the mixed molybdenum powder is coated through a chemical method, and finally the high-dispersity silver-molybdenum electrical contact material is obtained through breakage, mixing of a forming agent, drying, removing of the forming agent and infiltration, but due to the fact that ball milling treatment procedures are added, the production period of a product is prolonged, the energy consumption is increased, and on the other hand, the performance of the obtained contact is still adversely affected due to new impurities brought in by the addition of the forming agent.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a method for manufacturing the LED display
The technical scheme adopted by the invention is as follows:
as a first aspect of the present invention, there is provided a method for preparing a silver molybdenum tungsten electrical contact material, comprising the steps of:
(1) Fully mixing molybdenum oxide, tungsten oxide and silver nitrate powder, adding ammonia water into the mixed powder under the condition of ultrasonic oscillation stirring until the mixed powder is completely dissolved, stopping adding the ammonia water, adding boiled deionized water into the dissolved solution, heating and stirring, adjusting the pH value to 7.5-8.5, adding oxalic acid under the condition of solution boiling, and adjusting the pH value to 3-6 to obtain a mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid;
(2) Drying the mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid to obtain mixed powder;
(3) Carrying out two-stage reduction treatment on the mixed powder in a reducing atmosphere to obtain silver-molybdenum-tungsten composite powder;
(4) Mechanically crushing the silver-molybdenum-tungsten composite powder to obtain refined silver-molybdenum-tungsten composite powder;
(5) Sintering and granulating the refined silver-molybdenum-tungsten composite powder in a reducing atmosphere, crushing and sphericizing the sintered composite powder, and sieving to obtain uniformly granulated silver-molybdenum-tungsten composite powder;
(6) And carrying out compression molding, sintering, infiltration and repressing treatment on the silver-molybdenum-tungsten composite powder with uniform granulation to obtain the silver-molybdenum-tungsten electric contact material.
Further, in the step (1), the tungsten oxide and molybdenum oxide powders have an average particle size of 20nm to 100nm.
Further, in the step (2), the temperature of the drying treatment is 100-150 ℃ and the drying time is 10-15 h.
Further, in the step (3), the two-stage reduction treatment specifically includes: the temperature of the first stage is 400-500 ℃ and the treatment time is 2-3 h; the temperature of the second stage is 800-900 ℃ and the treatment time is 3-4 h; the reducing atmosphere is hydrogen or ammonia decomposition gas.
Further, in the step (4), the mechanical crushing treatment adopts a crushing mode of nail disc grinding and crushing.
Further, in the step (5), the sintering granulation temperature is 700-850 ℃ and the sintering time is 1-5 h; the crushing and sphericizing treatment adopts dry particle composite equipment to treat the powder.
As a second aspect of the present invention, there is provided a silver molybdenum tungsten electrical contact material prepared by the preparation method as described above.
Further, the mass percentage of the molybdenum is 15-40 wt%;
the mass percentage of the tungsten is 15-30wt%;
the balance of silver.
The beneficial effects of the invention are as follows:
1. compared with the traditional powder metallurgy process for preparing the silver-molybdenum electrical contact material, the method has the advantages that the nucleation rate is quickened by utilizing the binary ionization and heterogeneous nucleation of oxalic acid, oxalic acid dissolved in water is separated out again and adsorbed by molybdic acid and tungstic acid particles, the molybdic acid and tungstic acid particles are isolated from each other, the growth of the molybdic acid and tungstic acid particles is avoided, and the agglomeration phenomenon of dispersion strengthening phase elements is effectively restrained.
2. The silver-molybdenum-tungsten composite powder prepared by the invention is subjected to high-energy crushing treatment by the nail disc mill, and the nail disc mill pulverizer adopts a stacked pulverizing mode in the pulverizing process, so that materials can be fully mixed and ground in, and more uniform composite powder is obtained. Can effectively reduce the air hole defect existing in the powder particles in the traditional powder preparation process.
3. The invention adopts dry particle composite equipment to carry out sphericizing treatment on the powder, the form of the powder particles is spherical or approximately spherical, the edges and corners on the surfaces of the powder particles are eliminated, and the friction force among the powder particles is small in the process of filling the die cavity in a flowing way, so that the powder has good fluidity; through the sphericizing treatment of the powder particles, the fluidity and the filling property of the powder particles are improved, the pore size distribution of an infiltration channel in the primary pressed compact is uniform and communicated with each other, and liquid silver can be uniformly infiltrated as a filling material in the infiltration process, so that the hole defect in the electrical contact material can be effectively eliminated, and the density of the electrical contact material is improved.
4. According to the invention, tungsten and molybdenum are added into a silver matrix as reinforcing items, and the tungsten and the molybdenum can be in solid solution in any proportion, and the performances of the material in the aspects of conductivity, burning resistance, corrosion resistance and the like are improved due to the solid solution strengthening of the molybdenum and the tungsten.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a process flow diagram of the preparation method of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1:
(1) Fully mixing 20% molybdenum trioxide and 20% tungsten trioxide with the balance of silver nitrate, adding ammonia water into the mixed powder under the condition of ultrasonic oscillation stirring until the mixed powder is completely dissolved, stopping adding the ammonia water, adding boiled deionized water into a dissolved solution, heating and stirring, regulating the pH value to 7.5-8.5, and adding oxalic acid under the condition of solution boiling to regulate the pH value to 3-6; obtaining silver molybdate, silver tungstate, molybdic acid and tungstic acid mixed precipitate;
(2) Drying the mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid for 10 hours at the temperature of 100 ℃, and carrying out two-stage reduction treatment on the prepared mixed powder in a reducing atmosphere, wherein the temperature of the first stage is 400 ℃ and the treatment time is 2 hours; the temperature of the second stage is 800 ℃, and the treatment time is 3 hours; obtaining silver-molybdenum-tungsten composite powder;
(3) Performing high-energy crushing treatment on the silver-molybdenum-tungsten composite powder by nailing and disc grinding to obtain refined silver-molybdenum-tungsten composite powder;
(4) Sintering and granulating the refined silver-molybdenum-tungsten composite powder in a reducing atmosphere, wherein the sintering temperature is 700 ℃ and the sintering time is 1.5h; the sintered composite powder is subjected to sphericizing treatment by dry particle composite equipment, and then is sieved to 80 meshes; obtaining silver-molybdenum-tungsten composite powder with uniform granulation;
(5) And carrying out compression molding, sintering, infiltration and repressing treatment on the silver-molybdenum-tungsten composite powder with uniform granulation to obtain the silver-molybdenum-tungsten electric contact material.
Example 2:
(1) Fully mixing 30% molybdenum trioxide and 20% tungsten trioxide with the balance of silver nitrate, adding ammonia water into the mixed powder under the condition of ultrasonic oscillation stirring until the mixed powder is completely dissolved, stopping adding the ammonia water, adding boiled deionized water into a dissolved solution, heating and stirring, regulating the pH value to 7.5-8.5, and adding oxalic acid under the condition of solution boiling to regulate the pH value to 3-6; obtaining silver molybdate, silver tungstate, molybdic acid and tungstic acid mixed precipitate;
(2) Drying the mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid for 12 hours at 120 ℃, and carrying out two-stage reduction treatment on the prepared mixed powder in a reducing atmosphere, wherein the temperature of the first stage is 450 ℃, and the treatment time is 2.5 hours; the temperature of the second stage is 850 ℃ and the treatment time is 3.5 hours; obtaining silver-molybdenum-tungsten composite powder;
(3) Performing high-energy crushing treatment on the silver-molybdenum-tungsten composite powder by nailing and disc grinding to obtain refined silver-molybdenum-tungsten composite powder;
(4) Sintering and granulating the refined silver-molybdenum-tungsten composite powder in a reducing atmosphere, wherein the sintering temperature is 800 ℃ and the sintering time is 2.5h; the sintered composite powder is subjected to sphericizing treatment by dry particle composite equipment, and then is sieved to 80 meshes; obtaining silver-molybdenum-tungsten composite powder with uniform granulation;
(5) And carrying out compression molding, sintering, infiltration and repressing treatment on the silver-molybdenum-tungsten composite powder with uniform granulation to obtain the silver-molybdenum-tungsten electric contact material.
Example 3:
(1) Fully mixing 40% molybdenum trioxide (weight ratio) and 20% tungsten trioxide (weight ratio) with the balance of silver nitrate, adding ammonia water into the mixed powder under the condition of ultrasonic oscillation stirring until the mixed powder is completely dissolved, stopping adding ammonia water, adding boiled deionized water into a dissolved solution, heating and stirring, regulating the pH value to 7.5-8.5, and adding oxalic acid under the condition of solution boiling to regulate the pH value to 3-6; obtaining silver molybdate, silver tungstate, molybdic acid and tungstic acid mixed precipitate;
(2) Drying the mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid for 15 hours at 150 ℃, and carrying out two-stage reduction treatment on the prepared mixed powder in a reducing atmosphere, wherein the temperature of the first stage is 500 ℃ and the treatment time is 3 hours; the temperature of the second stage is 900 ℃, and the treatment time is 4 hours; obtaining silver-molybdenum-tungsten composite powder;
(3) Performing high-energy crushing treatment on the silver-molybdenum-tungsten composite powder by nailing and disc grinding to obtain refined silver-molybdenum-tungsten composite powder;
(4) Sintering and granulating the refined silver-molybdenum-tungsten composite powder in a reducing atmosphere, wherein the sintering temperature is 850 ℃ and the sintering time is 5 hours; the sintered composite powder is subjected to sphericizing treatment by dry particle composite equipment, and then is sieved to 80 meshes; obtaining silver-molybdenum-tungsten composite powder with uniform granulation;
(5) And carrying out compression molding, sintering, infiltration and repressing treatment on the silver-molybdenum-tungsten composite powder with uniform granulation to obtain the silver-molybdenum-tungsten electric contact material.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (8)
1. The preparation method of the silver-molybdenum-tungsten electric contact material is characterized by comprising the following steps of:
(1) Fully mixing molybdenum oxide, tungsten oxide and silver nitrate powder, adding ammonia water into the mixed powder under the condition of ultrasonic oscillation stirring until the mixed powder is completely dissolved, stopping adding the ammonia water, adding boiled deionized water into the dissolved solution, heating and stirring, adjusting the pH value to 7.5-8.5, adding oxalic acid under the condition of solution boiling, and adjusting the pH value to 3-6 to obtain a mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid;
(2) Drying the mixed precipitate of silver molybdate, silver tungstate, molybdic acid and tungstic acid to obtain mixed powder;
(3) Carrying out two-stage reduction treatment on the mixed powder in a reducing atmosphere to obtain silver-molybdenum-tungsten composite powder;
(4) Mechanically crushing the silver-molybdenum-tungsten composite powder to obtain refined silver-molybdenum-tungsten composite powder;
(5) Sintering and granulating the refined silver-molybdenum-tungsten composite powder in a reducing atmosphere, crushing and sphericizing the sintered composite powder, and sieving to obtain uniformly granulated silver-molybdenum-tungsten composite powder;
(6) And carrying out compression molding, sintering, infiltration and repressing treatment on the silver-molybdenum-tungsten composite powder with uniform granulation to obtain the silver-molybdenum-tungsten electric contact material.
2. The method for producing a silver-molybdenum-tungsten electrical contact material according to claim 1, wherein in the step (1), the average particle size of the tungsten oxide and molybdenum oxide powder is 20nm to 100nm.
3. The method according to claim 1, wherein in the step (2), the drying treatment is performed at a temperature of 100 to 150 ℃ for a drying time of 10 to 15 hours.
4. The method for preparing a silver-molybdenum-tungsten electrical contact material according to claim 1, wherein in step (3), the two-stage reduction treatment is specifically: the temperature of the first stage is 400-500 ℃ and the treatment time is 2-3 h; the temperature of the second stage is 800-900 ℃ and the treatment time is 3-4 h; the reducing atmosphere is hydrogen or ammonia decomposition gas.
5. The method according to claim 1, wherein in the step (4), the mechanical crushing treatment adopts a crushing mode of nail plate grinding.
6. The method for preparing a silver-molybdenum-tungsten electrical contact material according to claim 1, wherein in the step (5), the sintering granulation temperature is 700-850 ℃ and the sintering time is 1-5 h; the crushing and sphericizing treatment adopts dry particle composite equipment to treat the powder.
7. A silver molybdenum tungsten electrical contact material prepared by the method of any of claims 1-6.
8. A silver molybdenum tungsten electrical contact material according to claim 7, wherein,
the mass percentage of the molybdenum is 15-40 wt%;
the mass percentage of the tungsten is 15-30wt%;
the balance of silver.
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