CN111647829B - Preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy - Google Patents
Preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy Download PDFInfo
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- CN111647829B CN111647829B CN202010470174.XA CN202010470174A CN111647829B CN 111647829 B CN111647829 B CN 111647829B CN 202010470174 A CN202010470174 A CN 202010470174A CN 111647829 B CN111647829 B CN 111647829B
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- 239000002245 particle Substances 0.000 title claims abstract description 70
- IVQODXYTQYNJFI-UHFFFAOYSA-N oxotin;silver Chemical compound [Ag].[Sn]=O IVQODXYTQYNJFI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 52
- 239000011259 mixed solution Substances 0.000 claims description 47
- 239000002244 precipitate Substances 0.000 claims description 42
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 230000002431 foraging effect Effects 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- KKHJTSPUUIRIOP-UHFFFAOYSA-J tetrachlorostannane;hydrate Chemical compound O.Cl[Sn](Cl)(Cl)Cl KKHJTSPUUIRIOP-UHFFFAOYSA-J 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 5
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003466 welding 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
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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
- H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
- H01H1/02376—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te containing as major component SnO2
-
- 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
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Abstract
The invention discloses a preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy, which is implemented according to the following steps: step 1, preparing tin oxide whiskers; step 2, preparing tin oxide particles; step 3, preparing whisker particle hybrid reinforced silver-tin oxide composite powder by using tin oxide whiskers and particles; step 4, preparing whisker particle hybrid reinforced silver-based electric contact alloy by using the silver-tin oxide composite powder; the preparation method of the whisker particle hybrid reinforced silver tin oxide electric contact alloy can control the form of tin oxide in a silver matrix, improve the dispersibility of second-phase tin oxide in the silver matrix and ensure that second-phase oxides in the alloy are uniformly distributed; and because of the skeleton constraint action of the tin oxide whisker in the silver tin oxide electric contact material, the uniformity of a second phase can be maintained under the action of arc erosion, so that the performance and the service life of the silver tin oxide electric contact alloy are improved.
Description
Technical Field
The invention belongs to the technical field of alloy material preparation, and particularly relates to a preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy.
Background
Electric contact materialThe material and elements are the core material and elements of electronic industry such as electrical switches, instruments and meters, and mainly play the roles of connecting and disconnecting circuits and load current, and the quality of the performance directly influences the reliable operation and the service life of the switching electrical appliance. AgSnO2Is an environment-friendly electric contact material with great development prospect which is currently used for replacing toxic electric contact materials, and has already been researched and applied to a certain extent in the aspect of low-voltage electric appliances. AgSnO2As a metal matrix composite, the size, the morphology, the wettability with metal and the distribution state in a matrix of the reinforcing phase have great influence on the performance of the composite.
At present, researchers at home and abroad improve AgSnO in the following ways2The performance of the electric contact material is as follows: 1. AgSnO reduction by introduction of trace additives2Contact resistance, improvement of liquid Ag to SnO2Decrease SnO2The agglomeration probability is reduced, so that the arc erosion resistance and the fusion welding resistance of the electric contact material are effectively enhanced; 2. for SnO by chemical plating method2The surface of the particles is coated with Ag to improve the reinforcing phase SnO2Wettability with matrix Ag; 3. using SnO2Increasing SnO by nanocrystallization2The contact area of the particles and the matrix Ag is used for improving the mechanical property of the composite material, reducing the contact resistance and improving the electric arc resistance. Although the method can effectively improve AgSnO2The properties of the electric contact material, but the second phase oxide SnO is easy to appear2The tin oxide floats on the surface of a silver molten pool under the action of electric arc for many times, and the tin oxide is enriched again to generate segregation, so that the problems of increased contact resistance, higher temperature rise and the like of a contact material are caused, and the service performance and the service life of the contact material are seriously influenced.
Disclosure of Invention
The invention aims to provide a preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy, which can improve the arc erosion resistance and the service life of the silver tin oxide electric contact alloy.
The invention adopts the technical scheme that a preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy is implemented according to the following steps:
step 1, preparing tin oxide whiskers;
step 2, preparing tin oxide particles;
step 3, preparing whisker particle hybrid reinforced silver-tin oxide composite powder by using tin oxide whiskers and particles;
and 4, preparing the whisker particle hybrid reinforced silver-based electric contact alloy by using the silver-tin oxide composite powder.
The invention is also characterized in that:
the specific process of the step 1 is as follows:
step 1.1, dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol, and dropwise adding a sodium hydroxide solution with the concentration of 0.8-1mol/L into the mixed solution of tin chloride under the condition of magnetic stirring to obtain a mixed solution A;
step 1.2, adding hexadecyl trimethyl ammonium bromide into the mixed solution A and fully stirring to obtain precursor solution;
step 1.3, transferring the precursor liquid into a ground conical flask, and placing the ground conical flask into a constant-temperature water bath kettle for aging to obtain a mixed liquid B;
and step 1.4, performing suction filtration on the mixed solution B for multiple times until the solution is clear and has no foam, taking out a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain the tin oxide whisker.
Dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol in the step 1.1 to obtain a 0.2-0.3mol/L mixed solution of tin chloride, wherein the molar ratio of the hydrated tin chloride to sodium hydroxide is 1: 6-8; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.8-1.0.
In the step 1.2, the concentration of hexadecyl trimethyl ammonium bromide in the precursor solution is 0.1-0.2 mol/L.
In the step 1.3, the aging temperature is 80-90 ℃, and the aging time is 4-6 h.
The specific process of the step 2 is as follows:
step 2.1, fully dissolving tin chloride hydrate in deionized water to prepare a tin chloride solution with the concentration of 1-1.5 mol/L;
step 2.2, adding polyethylene glycol into the tin chloride solution, and uniformly stirring to obtain a mixed solution C with the concentration of the polyethylene glycol solution being 0.3-0.6 mol/L;
step 2.3, dropwise adding ammonia water with the concentration of 0.6-1.0mol/L into the mixed solution C, continuously stirring until complete precipitation is achieved, standing for precipitation for 2 hours, layering the solution, and pouring out supernatant to obtain a precipitate;
and 2.4, carrying out suction filtration on the precipitate for multiple times until silver nitrate detects that the solution in the filter flask does not contain chloride ions, then placing the suction-filtered precipitate on a watch glass, drying the precipitate in a vacuum box at 80 ℃ to constant weight, fully grinding the precipitate, drying the precipitate again, and then placing the precipitate in a muffle furnace for high-temperature sintering to obtain the tin oxide powder.
The high-temperature sintering process of putting the raw materials into a muffle furnace comprises the following steps: the temperature in the muffle furnace is adjusted to be 500 ℃, and the temperature is kept for 2 h.
The specific process of the step 3 is as follows: mixing tin oxide whiskers and tin oxide particles according to a mass ratio of 1:1-3 to obtain a mixture, placing silver powder and the mixture in a horizontal planetary ball mill according to a mass ratio of 88:12 to fully mix, and annealing in a vacuum atmosphere at the annealing temperature of 400 ℃ and the annealing time of 600 ℃ for 2-4 hours to obtain uniformly mixed whisker particle hybrid reinforced silver-tin oxide composite powder.
The technical parameters of the ball milling in the horizontal planetary ball mill are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are 15mm, 10mm and 6mm respectively, the quantity ratio is 1:3:1, the ball-material ratio is 10-15:1, the ball-milling rotation speed is 400-600r/min, and the ball-milling time is 4-6 h.
The specific process of the step 4 is as follows: and pressing, sintering and extruding the whisker particle hybrid reinforced silver-tin oxide composite powder to obtain the whisker particle hybrid reinforced silver-based electric contact alloy.
The invention has the beneficial effects that:
the invention relates to a preparation method of a whisker particle mixed reinforced silver tin oxide electric contact alloy, which takes tin chloride hydrate as a tin source and Cetyl Trimethyl Ammonium Bromide (CTAB) as a surfactant, and obtains tin oxide whiskers after aging, suction filtration and vacuum drying; and adjusting the pH value by ammonia water by a chemical coprecipitation method, preparing tin oxide particles by using polyethylene glycol as a dispersing agent, and obtaining whisker particle hybrid reinforced silver-tin oxide composite powder by high-energy ball milling so as to prepare the whisker particle hybrid reinforced silver-based electric contact alloy. The tin oxide whisker has the characteristics of high strength, high modulus, good heat resistance, good compatibility and the like, can effectively reduce the formation of defects in the silver-based electric contact alloy, and can effectively improve the mechanical property and the physical property of the silver-based electric contact alloy. The second phase oxide in the alloy is tin oxide microsphere particles and tin oxide whiskers with larger length-diameter ratio, the oxides are uniformly distributed, the dispersibility of the second phase tin oxide in a silver matrix is improved, and due to the skeleton constraint effect of the tin oxide whiskers in the silver tin oxide electric contact material, the obtained whisker particle hybrid reinforced silver-based electric contact material can effectively avoid the situation that the second phase tin oxide is difficult to suspend in a liquid silver molten pool and is separated from the silver matrix and enriched on the surface of a contact, so that the uniformity of the second phase can be maintained under the action of arc erosion, and the performance and the service life of the silver tin oxide electric contact alloy are greatly improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of whisker particle mixed reinforced silver tin oxide electric contact alloy, which is implemented according to the following steps:
step 1, preparing tin oxide whiskers; the specific process is as follows:
step 1.1, dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a 0.2-0.3mol/L tin chloride mixed solution, and dropwise adding a 0.8-1mol/L sodium hydroxide solution into the tin chloride mixed solution under the condition of magnetic stirring to obtain a mixed solution A;
wherein the molar ratio of the hydrated tin chloride to the sodium hydroxide is 1: 6-8; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.8-1.0.
Step 1.2, adding hexadecyl trimethyl ammonium bromide into the mixed solution A and fully stirring to obtain precursor solution; the concentration of hexadecyl trimethyl ammonium bromide in the precursor liquid is 0.1-0.2 mol/L;
step 1.3, transferring the precursor liquid into a ground conical flask, and placing the ground conical flask into a constant-temperature water bath kettle for aging at the aging temperature of 80-90 ℃ for 4-6h to obtain a mixed liquid B;
step 1.4, performing suction filtration on the mixed solution B for multiple times until the solution is clear and has no foam, taking out a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain tin oxide whiskers;
step 2, preparing tin oxide particles; the specific process is as follows:
step 2.1, fully dissolving tin chloride hydrate in deionized water to prepare a tin chloride solution with the concentration of 1-1.5 mol/L;
step 2.2, adding polyethylene glycol into the tin chloride solution, and uniformly stirring to obtain a mixed solution C with the concentration of the polyethylene glycol solution being 0.3-0.6 mol/L;
step 2.3, dropwise adding ammonia water with the concentration of 0.6-1.0mol/L into the mixed solution C, continuously stirring until complete precipitation is achieved, standing for precipitation for 2 hours, layering the solution, and pouring out supernatant to obtain a precipitate;
2.4, carrying out suction filtration on the precipitate for multiple times until silver nitrate detects that the solution in the filter flask does not contain chloride ions, then placing the suction-filtered precipitate on a watch glass, drying the precipitate in a vacuum box at 80 ℃ to constant weight, fully grinding the precipitate, drying the precipitate again, then placing the precipitate into a muffle furnace for high-temperature sintering, adjusting the temperature in the muffle furnace to be 500 ℃, and preserving the heat for 2 hours to obtain tin oxide powder;
step 3, preparing whisker particle hybrid reinforced silver-tin oxide composite powder by using tin oxide whiskers and particles; the specific process is as follows: mixing tin oxide whiskers and tin oxide particles according to a mass ratio of 1:1-3 to obtain a mixture, placing silver powder and the mixture in a horizontal planetary ball mill according to a mass ratio of 88:12 to fully mix, and annealing in a vacuum atmosphere at the annealing temperature of 400 ℃ and the annealing time of 600 ℃ for 2-4 hours to obtain uniformly mixed whisker particle hybrid reinforced silver-tin oxide composite powder.
The technical parameters of the ball milling in the horizontal planetary ball mill are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are 15mm, 10mm and 6mm respectively, the quantity ratio is 1:3:1, the ball-material ratio is 10-15:1, the ball-milling rotation speed is 400-600r/min, and the ball-milling time is 4-6 h.
And 4, pressing, sintering and extruding the whisker particle hybrid reinforced silver-tin oxide composite powder to obtain the whisker particle hybrid reinforced silver-based electric contact alloy.
Example 1
A preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy is implemented according to the following steps:
dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution with the tin chloride content of 0.2mol/L, and dropwise adding a sodium hydroxide solution with the concentration of 0.8mol/L into the mixed solution of tin chloride under the condition of magnetic stirring to obtain a mixed solution A; wherein the molar ratio of the hydrated tin chloride to the sodium hydroxide is 1: 6; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.8; adding cetyl trimethyl ammonium bromide into the mixed solution A and fully stirring to obtain precursor solution with the concentration of the cetyl trimethyl ammonium bromide being 0.1 mol/L; transferring the precursor liquid into a ground conical flask, and placing the ground conical flask into a constant-temperature water bath kettle for aging at the aging temperature of 80 ℃ for 4 hours to obtain a mixed liquid B; carrying out suction filtration on the mixed solution B for many times until the solution is clear and has no foam, taking out a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain tin oxide whiskers;
fully dissolving hydrated tin chloride in deionized water to prepare a tin chloride solution with the concentration of 1 mol/L; adding polyethylene glycol into the tin chloride solution, and uniformly stirring to obtain a mixed solution C with the concentration of the polyethylene glycol solution being 0.3 mol/L; dropwise adding 0.6mol/L ammonia water into the mixed solution C and continuously stirring until complete precipitation, standing for precipitation for 2 hours, then layering the solution, and pouring out supernatant to obtain a precipitate; carrying out suction filtration on the precipitate for multiple times until silver nitrate detects that the solution in the suction filter flask does not contain chloride ions, then placing the suction-filtered precipitate on a watch glass, drying the precipitate in a vacuum box at 80 ℃ to constant weight, fully grinding the precipitate, drying the precipitate again, then placing the precipitate into a muffle furnace for high-temperature sintering, adjusting the temperature in the muffle furnace to be 500 ℃, and preserving the heat for 2 hours to obtain tin oxide powder;
and (2) putting the tin oxide whiskers, the tin oxide particles and the silver powder in a horizontal planetary ball mill according to the mass ratio of 6:6:88 for fully mixing, and annealing in a vacuum atmosphere at the annealing temperature of 400 ℃ for 2 hours to obtain the uniformly mixed whisker particle hybrid reinforced silver-tin oxide composite powder.
The technical parameters of the ball milling in the horizontal planetary ball mill are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are 15mm, 10mm and 6mm respectively, the grinding balls are proportioned according to the quantity ratio of 1:3:1, the ball-material ratio is 10:1, the ball-milling rotating speed is 400r/min, and the ball-milling time is 4 hours.
Mixing crystal whisker particles with reinforced silver-tin oxide composite powder, pressing, sintering and extruding to obtain Ag88 SnO with the mass ratio of tin oxide crystal whisker to tin oxide particles being 1:1212 the whisker particle intermixing enhances silver-based electrical contact alloys.
Example 2
A preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy is implemented according to the following steps:
dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution with the tin chloride content of 0.25mol/L, and dropwise adding a sodium hydroxide solution with the concentration of 0.9mol/L into the mixed solution of tin chloride under the condition of magnetic stirring to obtain a mixed solution A; wherein the molar ratio of the hydrated tin chloride to the sodium hydroxide is 1: 7; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.9; adding hexadecyl trimethyl ammonium bromide into the mixed solution A and fully stirring to obtain precursor solution; the concentration of hexadecyl trimethyl ammonium bromide in the precursor liquid is 0.15 mol/L; transferring the precursor liquid into a ground conical flask, and placing the ground conical flask into a constant-temperature water bath kettle for aging at the aging temperature of 85 ℃ for 5 hours to obtain a mixed liquid B; carrying out suction filtration on the mixed solution B for many times until the solution is clear and has no foam, taking out a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain tin oxide whiskers;
fully dissolving hydrated tin chloride in deionized water to prepare a tin chloride solution with the concentration of 1.25 mol/L; adding polyethylene glycol into the tin chloride solution, and uniformly stirring to obtain a mixed solution C with the concentration of the polyethylene glycol solution being 0.45 mol/L; dropwise adding 0.8mol/L ammonia water into the mixed solution C, continuously stirring until complete precipitation is achieved, standing for precipitation for 2 hours, layering the solution, and pouring out supernatant to obtain a precipitate; carrying out suction filtration on the precipitate for multiple times until silver nitrate detects that the solution in the suction filter flask does not contain chloride ions, then placing the suction-filtered precipitate on a watch glass, drying the precipitate in a vacuum box at 80 ℃ to constant weight, fully grinding the precipitate, drying the precipitate again, then placing the precipitate into a muffle furnace for high-temperature sintering, adjusting the temperature in the muffle furnace to be 500 ℃, and preserving the heat for 2 hours to obtain tin oxide powder;
and (2) putting the tin oxide whiskers, the tin oxide particles and the silver powder in a horizontal planetary ball mill according to the mass ratio of 4:8:88 for fully mixing, and annealing in a vacuum atmosphere at the annealing temperature of 500 ℃ for 3 hours to obtain the uniformly mixed whisker particle hybrid reinforced silver-tin oxide composite powder.
The technical parameters of the ball milling in the horizontal planetary ball mill are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are 15mm, 10mm and 6mm respectively, the grinding balls are proportioned according to the quantity ratio of 1:3:1, the ball-material ratio is 12:1, the ball-milling rotating speed is 500r/min, and the ball-milling time is 5 hours.
Mixing crystal whisker particles with reinforced silver-tin oxide composite powder, pressing, sintering and extruding to obtain Ag88 SnO with the mass ratio of tin oxide crystal whisker to tin oxide particles being 1:2212 the whisker particle intermixing enhances silver-based electrical contact alloys.
Example 3
A preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy is implemented according to the following steps:
dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution with the tin chloride content of 0.3mol/L, and dropwise adding the solution with the concentration of 1mol/L into the mixed solution of tin chloride under the condition of magnetic stirring to obtain a mixed solution A; wherein the molar ratio of the hydrated tin chloride to the sodium hydroxide is 1: 8; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1; adding hexadecyl trimethyl ammonium bromide into the mixed solution A and fully stirring to obtain precursor solution; the concentration of hexadecyl trimethyl ammonium bromide in the precursor liquid is 0.2 mol/L; transferring the precursor liquid into a ground conical flask, and placing the ground conical flask into a constant-temperature water bath kettle for aging at the aging temperature of 90 ℃ for 6 hours to obtain a mixed liquid B; carrying out suction filtration on the mixed solution B for many times until the solution is clear and has no foam, taking out a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain tin oxide whiskers;
fully dissolving hydrated tin chloride in deionized water to prepare a tin chloride solution with the concentration of 1.5 mol/L; adding polyethylene glycol into the tin chloride solution, and uniformly stirring to obtain a mixed solution C with the concentration of the polyethylene glycol solution being 0.6 mol/L; dropwise adding 1.0mol/L ammonia water into the mixed solution C, continuously stirring until complete precipitation, standing for precipitation for 2 hours, layering the solution, and pouring out supernatant to obtain precipitate; carrying out suction filtration on the precipitate for multiple times until silver nitrate detects that the solution in the suction filter flask does not contain chloride ions, then placing the suction-filtered precipitate on a watch glass, drying the precipitate in a vacuum box at 80 ℃ to constant weight, fully grinding the precipitate, drying the precipitate again, then placing the precipitate into a muffle furnace for high-temperature sintering, adjusting the temperature in the muffle furnace to be 500 ℃, and preserving the heat for 2 hours to obtain tin oxide powder;
and (2) putting the tin oxide whiskers, the tin oxide particles and the silver powder in a horizontal planetary ball mill according to the mass ratio of 3:9:88 for fully mixing, and annealing in a vacuum atmosphere at the annealing temperature of 600 ℃ for 4 hours to obtain the uniformly mixed whisker particle hybrid reinforced silver-tin oxide composite powder.
The technical parameters of the ball milling in the horizontal planetary ball mill are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are 15mm, 10mm and 6mm respectively, and the grinding balls are mixed according to the quantity ratio of 1:3:1, the ball material ratio is 15:1, ball milling rotation speed of 600r/min and ball milling time of 6 h.
Mixing crystal whisker particles with reinforced silver-tin oxide composite powder, pressing, sintering and extruding to obtain Ag88 SnO with the mass ratio of tin oxide crystal whisker to tin oxide particles being 1:3212 the whisker particle intermixing enhances silver-based electrical contact alloys.
According to the preparation method of the whisker particle hybrid reinforced silver tin oxide electric contact alloy, tin chloride hydrate is used as a tin source, Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a surfactant, and tin oxide whiskers are obtained through aging, suction filtration and vacuum drying; and adjusting the pH value by ammonia water by a chemical coprecipitation method, preparing tin oxide particles by using polyethylene glycol as a dispersing agent, and obtaining whisker particle hybrid reinforced silver-tin oxide composite powder by high-energy ball milling so as to prepare the whisker particle hybrid reinforced silver-based electric contact alloy. The tin oxide whisker has the characteristics of high strength, high modulus, good heat resistance, good compatibility and the like, can effectively reduce the formation of defects in the silver-based electric contact alloy, and can effectively improve the mechanical property and the physical property of the silver-based electric contact alloy. The second phase oxide in the alloy is tin oxide microsphere particles and tin oxide whiskers with larger length-diameter ratio, the oxides are uniformly distributed, the dispersibility of the second phase tin oxide in a silver matrix is improved, and due to the skeleton constraint effect of the tin oxide whiskers in the silver tin oxide electric contact material, the obtained whisker particle hybrid reinforced silver-based electric contact material can effectively avoid the situation that the second phase tin oxide is difficult to suspend in a liquid silver molten pool and is separated from the silver matrix and enriched on the surface of a contact, so that the uniformity of the second phase can be maintained under the action of arc erosion, and the performance and the service life of the silver tin oxide electric contact alloy are greatly improved.
Claims (3)
1. A preparation method of whisker particle hybrid reinforced silver tin oxide electric contact alloy is characterized by comprising the following steps:
step 1, preparing tin oxide whiskers; the specific process of the step 1 is as follows:
step 1.1, dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol, and dropwise adding a sodium hydroxide solution with the concentration of 0.8-1mol/L into the mixed solution of tin chloride under the condition of magnetic stirring to obtain a mixed solution A;
dissolving hydrated tin chloride in a mixed solution of deionized water and absolute ethyl alcohol in the step 1.1 to obtain a 0.2-0.3mol/L mixed solution of tin chloride, wherein the molar ratio of the hydrated tin chloride to sodium hydroxide is 1: 6-8; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.8-1.0;
step 1.2, adding hexadecyl trimethyl ammonium bromide into the mixed solution A and fully stirring to obtain precursor solution;
the concentration of hexadecyl trimethyl ammonium bromide in the precursor liquid is 0.1-0.2 mol/L;
step 1.3, transferring the precursor liquid into a ground conical flask, and placing the ground conical flask into a constant-temperature water bath kettle for aging to obtain a mixed liquid B;
step 1.4, performing suction filtration on the mixed solution B for multiple times until the solution is clear and has no foam, taking out a filter cake, and drying the filter cake in a vacuum oven to constant weight to obtain tin oxide whiskers;
step 2, preparing tin oxide particles; the specific process of the step 2 is as follows:
step 2.1, fully dissolving tin chloride hydrate in deionized water to prepare a tin chloride solution with the concentration of 1-1.5 mol/L;
step 2.2, adding polyethylene glycol into the tin chloride solution, and uniformly stirring to obtain a mixed solution C with the concentration of the polyethylene glycol solution being 0.3-0.6 mol/L;
step 2.3, dropwise adding ammonia water with the concentration of 0.6-1.0mol/L into the mixed solution C, continuously stirring until complete precipitation is achieved, standing for precipitation for 2 hours, layering the solution, and pouring out supernatant to obtain a precipitate;
2.4, carrying out suction filtration on the precipitate for multiple times until silver nitrate detects that the solution in the filter flask does not contain chloride ions, then placing the suction-filtered precipitate on a watch glass, drying the precipitate in a vacuum box at 80 ℃ to constant weight, fully grinding the precipitate, drying the precipitate again, and then placing the precipitate into a muffle furnace for high-temperature sintering to obtain tin oxide powder;
the high-temperature sintering process of putting into a muffle furnace is as follows: adjusting the temperature in the muffle furnace to 500 ℃, and preserving the temperature for 2 h;
step 3, preparing whisker particle hybrid reinforced silver-tin oxide composite powder by using tin oxide whiskers and particles; the specific process of the step 3 is as follows: firstly mixing tin oxide whiskers and tin oxide particles according to the mass ratio of 1:1-3 to obtain a mixture, putting silver powder and the mixture in a horizontal planetary ball mill according to the mass ratio of 88:12 for fully mixing, and annealing in a vacuum atmosphere at the annealing temperature of 400 ℃ and the annealing time of 600 ℃ for 2-4h to obtain uniformly mixed whisker particle hybrid reinforced silver-tin oxide composite powder;
the technical parameters of the ball milling in the horizontal planetary ball mill are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are 15mm, 10mm and 6mm respectively, the quantity ratio is 1:3:1, the ball-material ratio is 10-15:1, the ball-milling rotation speed is 400-;
and 4, preparing the whisker particle hybrid reinforced silver-based electric contact alloy by using the silver-tin oxide composite powder.
2. The method for preparing a whisker particle hybrid reinforced silver tin oxide electrical contact alloy as claimed in claim 1, wherein the aging temperature in step 1.3 is 80-90 ℃ and the aging time is 4-6 h.
3. The method for preparing the whisker particle hybrid reinforced silver tin oxide electrical contact alloy as claimed in claim 1, wherein the step 4 comprises the following specific processes: and pressing, sintering and extruding the whisker particle hybrid reinforced silver-tin oxide composite powder to obtain the whisker particle hybrid reinforced silver-based electric contact alloy.
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