CN117102479B - Preparation process of modified silver tin oxide and prepared modified silver tin oxide - Google Patents
Preparation process of modified silver tin oxide and prepared modified silver tin oxide Download PDFInfo
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- CN117102479B CN117102479B CN202311344878.2A CN202311344878A CN117102479B CN 117102479 B CN117102479 B CN 117102479B CN 202311344878 A CN202311344878 A CN 202311344878A CN 117102479 B CN117102479 B CN 117102479B
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- tin oxide
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- silver
- silver tin
- amphoteric
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- IVQODXYTQYNJFI-UHFFFAOYSA-N oxotin;silver Chemical class [Ag].[Sn]=O IVQODXYTQYNJFI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000001238 wet grinding Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 37
- 229920002472 Starch Polymers 0.000 claims abstract description 35
- 235000019698 starch Nutrition 0.000 claims abstract description 35
- 239000008107 starch Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000005324 oxide salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- 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
- B22F1/12—Metallic powder containing non-metallic 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G5/00—Compounds of silver
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation process of modified silver tin oxide and the prepared modified silver tin oxide, and relates to the field of powder metallurgy. Wherein, a preparation process of the modified silver tin oxide comprises the following steps: uniformly stirring a salt crystal solution of the amphoteric oxide and a silver nitrate crystal solution to prepare a mixed solution; adding carbonate solution into the mixed solution to prepare coprecipitated starch; washing, primary drying, calcining, primary wet grinding and secondary drying are sequentially carried out on the coprecipitated starch body, so that silver oxide doped with amphoteric oxide is obtained; mixing the silver tin oxide base powder prepared by the coating method with silver oxide doped with amphoteric oxide, performing secondary wet grinding, and then drying to obtain the modified silver tin oxide. When the process is used for preparing the modified silver tin oxide doped with the amphoteric oxide, a large amount of ammonia water is not required to be doped, and the problem that the modified silver tin oxide doped with the amphoteric oxide is difficult to produce by the traditional coating method is solved.
Description
Technical Field
The invention relates to the field of powder metallurgy, in particular to a preparation process of modified silver tin oxide and the prepared modified silver tin oxide.
Background
Silver tin oxide material is the main stream material of silver-based electrical contact material adopted in the current piezoelectric device industry, and the current production of silver tin oxide mostly adopts the technological methods of alloy internal oxidation, powder pre-oxidation, chemical coating and the like.
With the continuous development of modern industry, the requirements of the diversification of the loading conditions on the material performance, in particular the requirements of mechanical properties and electrical properties, are also continuously improved. However, improving the performance characteristics of silver tin oxide materials requires doping with different types of oxides, such as Bi 2 O 3 、In 2 O 3 CuO, znO, beO, etc.
The method for preparing the alloy comprises the steps of preparing a metal alloy, adding silver, and carrying out the process of preparing the alloy, wherein the method for preparing the alloy comprises the steps of adding doped metal during smelting to realize the generation of an oxide at the later stage, wherein the doped metal is limited by melting with silver, and the added amount is limited by the content, so that the application of the alloy at a load application end is limited.
Chemical coating is a powder mixing process, but is superior to conventional powder mixing processes in terms of uniformity of powder mixing and bonding strength of the added oxide to the silver matrix, relative to conventional powder mixing processes. However, during the chemical coating phase, the silver ammonia solution contains a large amount of ammonia water, the solution is strongly alkaline, however, some oxides are amphoteric oxides, such as ZnO, al 2 O 3 BeO, etc., these amphoteric oxides cannot be doped directly in alkaline solutions, i.e. cannot be added directly during the coating phase.
It is therefore of great research importance how to provide a process that enables the uniform doping of amphoteric oxides into silver tin oxide.
Disclosure of Invention
In order to solve the problem that amphoteric oxides are difficult to uniformly dope into silver tin oxide in the related art, the application provides a preparation process of modified silver tin oxide and the prepared modified silver tin oxide.
In a first aspect, the preparation process of the modified silver tin oxide provided by the application adopts the following technical scheme:
a preparation process of modified silver tin oxide comprises the following steps:
uniformly stirring a salt crystal solution of the amphoteric oxide and a silver nitrate crystal solution to prepare a mixed solution;
adding carbonate solution into the mixed solution to prepare coprecipitated starch;
washing, primary drying, calcining, primary wet grinding and secondary drying are sequentially carried out on the coprecipitated starch body, so that silver oxide doped with amphoteric oxide is obtained;
mixing the silver tin oxide base powder prepared by the coating method with silver oxide doped with amphoteric oxide, performing secondary wet grinding, and then drying to obtain the modified silver tin oxide.
When the conventional coating method is used for producing the silver tin oxide base powder, a large amount of ammonia water is required, however, the amphoteric oxide can be dissolved in the ammonia water, so that the conventional coating method is difficult to produce the modified silver tin oxide doped with the amphoteric oxide.
In order to prepare the modified silver tin oxide doped with the amphoteric oxide so as to further improve the mechanical property and the electrical property of the silver tin oxide electrical contact material in the related technology, the inventor firstly adopts a coprecipitation method to prepare coprecipitated starch containing silver carbonate or hydroxide and amphoteric oxide carbonate or hydroxide, then carries out washing, primary drying, calcination, primary wet grinding and secondary drying on the coprecipitated starch to prepare the silver oxide doped with the amphoteric oxide, and finally carries out wet grinding on the silver tin oxide base powder prepared by the traditional coating method and the silver oxide doped with the amphoteric oxide to finally prepare the modified tin oxide doped with the amphoteric oxide.
When the process is adopted to prepare the modified silver tin oxide doped with the amphoteric oxide, a large amount of ammonia water is not required to be doped, the problem that the modified silver tin oxide doped with the amphoteric oxide is difficult to produce by a traditional coating method is solved, and when the modified silver tin oxide doped with the amphoteric oxide is produced, salt crystal solutions of different amphoteric oxides can be doped according to different performance requirements, so that the amphoteric oxide is doped into the silver tin oxide electrical contact material. The amphoteric oxide can be doped according to actual requirements, and has the characteristics of wide doping range and high amphoteric oxide conversion rate.
Secondly, compared with a process of directly mixing amphoteric oxides into silver tin oxide base powder by a powder mixing method, in the modified silver tin oxide prepared by the process, oxide particles are more uniform in silver base, the dispersibility of oxide is better, and the problems of microscopic powder agglomeration, poor uniformity of oxide distribution and microscopic segregation of oxide do not exist. And compared with the method for directly producing the modified silver tin oxide doped with the amphoteric oxide by adopting a soluble tin salt solution, a salt crystal solution of the amphoteric oxide and a silver nitrate crystal solution through a coprecipitation method (without mixing and ball milling of silver tin oxide base powder prepared by a coating method and silver oxide doped with the amphoteric oxide), the modified silver tin oxide has the characteristics of small tin oxide granularity and narrow distribution, is favorable for promoting the uniform distribution of tin oxide particles, and can further improve the electrical property of an electrical contact material.
In addition, in the process of preparing the modified silver tin oxide, twice wet milling is carried out, the primary wet milling step after the coprecipitated starch is omitted, the particle size difference of the silver oxide doped with the amphoteric oxide is large, and the dispersibility of the silver oxide doped with the amphoteric oxide in the silver tin oxide base powder is poor. And the secondary wet grinding step is omitted, so that the silver tin oxide base powder is easy to agglomerate, and the problem of poor dispersibility of the silver oxide doped with the amphoteric oxide in the silver tin oxide base powder can also occur.
Alternatively, the salt crystal solution of the amphoteric oxide is selected from soluble salt solutions of the amphoteric oxide, such as aluminum chloride solution, zinc nitrate solution, copper nitrate solution and the like.
Optionally, the carbonate solution is any one of sodium carbonate solution, ammonium carbonate solution and potassium carbonate solution.
Optionally, the mass concentration of the carbonate solution is 15-20%, and the adding speed of the carbonate solution is controlled to be 2-3L/min.
The mass concentration of the carbonate solution is 15-20%, and when the adding speed of the carbonate solution is controlled to be 2-3L/min, the generation rate of the coprecipitated starch is moderate, so that the coprecipitated starch with small and uniform granularity is obtained, and further the silver oxide doped with amphoteric oxide with small granularity and capable of being uniformly dispersed is obtained. Meanwhile, the method can promote the conversion of silver ions into silver carbonate or silver hydroxide and the conversion of the salt of the amphoteric oxide into carbonate or hydroxide of the amphoteric oxide, is beneficial to promoting the complete conversion of metal ions in the mixed solution into sediment, and finally improves the conversion rate of the amphoteric oxide and the silver oxide.
Optionally, the weight ratio of carbonate in the carbonate solution to silver nitrate in the silver nitrate crystal solution is (0.8-1.2): 1.
when the weight ratio of carbonate to silver nitrate is in the range, the silver ions and metal ions in the salt crystal solution of the amphoteric oxide can be completely converted into corresponding sediment, and the method has the characteristics of high conversion rate and small pollution.
Optionally, in the step of washing the coprecipitated starch, washing the coprecipitated starch with water until the pH of the washed water is within a range of 6.5-7.5, and stopping washing.
Optionally, the temperature of the primary drying is controlled between 100 ℃ and 120 ℃.
The coprecipitated starch is firstly dried at 100-120 ℃ before calcination, so that free moisture in the coprecipitated starch can be effectively removed, the problem of uneven local heating of the coprecipitated starch caused by overlarge moisture content in the coprecipitated starch is prevented, and the silver oxide doped with amphoteric oxide with uniform granularity and stable structural composition is obtained.
The calcination conditions of the optional coprecipitated starch are as follows: the calcination temperature is 680-720 ℃ and the calcination time is 5-7h.
The calcination temperature is controlled between 680 and 720 ℃, so that hydroxide precipitation or carbonate precipitation in coprecipitated starch can be completely converted into oxide, and meanwhile, the problem of transition sintering of silver oxide doped with amphoteric oxide is prevented.
Optionally, the rotating speed of the primary wet grinding is 80-90r/min, and the wet grinding time is 1-1.5h.
In order to improve the dispersibility of silver oxide doped with amphoteric oxide, the metal oxide obtained after calcination is wet-milled. Wherein, the wet milling is favorable for improving the fineness and uniformity of the granularity of the metal oxide, and the uniform dispersion of the silver oxide doped with the amphoteric oxide can be further improved when the rotating speed of the wet milling is controlled to be 80-90r/min and the time is controlled to be 1-1.5h.
Optionally, the temperature of the secondary drying is controlled between 100 ℃ and 120 ℃.
Because the calcined metal oxide adopts a wet milling ball milling mode, the calcined metal oxide needs to be dried, the drying temperature is controlled at 100-120 ℃, free moisture in coprecipitated starch can be effectively removed, and the silver oxide doped with amphoteric oxide can be uniformly dispersed in silver tin oxide base powder.
Optionally, the weight ratio of the silver tin oxide base powder to the silver oxide doped with the amphoteric oxide is 1: (0.006-0.02).
The weight ratio of the silver tin oxide base powder to the silver oxide doped with the amphoteric oxide is preferably controlled at 1: (0.006-0.02) can simultaneously improve the electrical property and the physical and mechanical properties of the modified silver tin oxide electrical contact material.
Optionally, the rotating speed of the secondary wet grinding is 80-90r/min, and the wet grinding time is 1-1.5h.
The rotating speed of the secondary wet grinding is controlled to be 80-90r/min, which is favorable for uniformly mixing the silver oxide doped with amphoteric oxide and the silver tin oxide base powder.
In a second aspect, the present application provides a modified silver tin oxide, which adopts the following technical scheme:
a modified silver tin oxide produced by the method for producing a modified silver tin oxide according to any one of the above.
The modified silver tin oxide doped with the amphoteric oxide has better electrical property and mechanical property.
In summary, the technical scheme of the application at least comprises the following beneficial effects:
1. when the process is adopted to prepare the modified silver tin oxide doped with the amphoteric oxide, a large amount of ammonia water is not required to be doped, the problem that the modified silver tin oxide doped with the amphoteric oxide is difficult to produce by a traditional coating method is solved, and when the modified silver tin oxide doped with the amphoteric oxide is produced, different salt crystal solutions of the amphoteric oxide can be doped according to different performance requirements, so that the amphoteric oxide is doped into the silver tin oxide electrical contact material. The amphoteric oxide can be doped according to actual requirements, and has the characteristics of wide doping range and high amphoteric oxide conversion rate.
2. Compared with the process of directly mixing the amphoteric oxide into the silver tin oxide base powder by the powder mixing method, in the modified silver tin oxide prepared by the process, oxide particles are more uniform in silver base, the dispersibility of oxide is better, and the problems of microscopic powder agglomeration, poor uniformity of oxide distribution and microscopic segregation of oxide do not exist.
3. Compared with the method for directly producing the modified silver tin oxide doped with the amphoteric oxide by adopting a soluble tin salt solution, an amphoteric oxide salt crystal solution and a silver nitrate crystal solution through a coprecipitation method (the silver tin oxide base powder prepared by a coating method and the silver oxide doped with the amphoteric oxide do not need to be subjected to blending ball milling), the modified silver tin oxide has the characteristics of small tin oxide granularity and narrow distribution, is favorable for promoting the uniform distribution of tin oxide particles, and can further improve the electrical property of an electrical contact material.
Drawings
Fig. 1 is a scanning electron microscope image of the modified silver tin oxide prepared in example 1 (2 μm, eht=20.00 kv, mag=3.00 kx, wd=9.5 mm, signala=ntsfsd).
Fig. 2 is a scanning electron microscope image of the modified silver tin oxide prepared in comparative example 1 (10 μm, eht=20.00 kv, mag=1.00 kx, wd=9.5 mm, signala=ntsfsd).
Description of the drawings: the black coarse particles in the matrix are zinc oxide, and the black fine particles are tin oxide.
Detailed Description
The present application is described in further detail below in connection with specific experiments.
Preparation example of silver tin oxide base powder
A silver tin oxide base powder is prepared by the following steps:
according to SnO 2 : 12kg of SnO is weighed according to the proportion of Ag=1.2:8.8 2 And 170.4kgAgNO 3 The method comprises the steps of carrying out a first treatment on the surface of the SnO is prepared 2 Adding 100kg of water to prepare suspension, and performing ultrasonic dispersion for 10min; preparing silver nitrate into silver ammonia solution with the concentration of 0.3mol/L, then, mixing the silver ammonia solution with the suspension, and stirring and dispersing the silver ammonia solution; 10kg of reducing agent triethanolamine and 1kg of dispersing agent are added and fully stirred for 30min; then adding sodium hydroxide to adjust the pH of the reaction system to 10; heating to 50 ℃ for reaction for 2 hours, filtering out precipitate, washing the precipitate to be neutral, and then drying and roasting to obtain silver tin oxide basic powder AgSnO 2 。
Examples
[ example 1 ]
A preparation process of modified silver tin oxide comprises the following steps:
s1, uniformly stirring 2.7kg of zinc nitrate solution with the mass concentration of 25% and 4.4kg of silver nitrate solution with the mass concentration of 25% to prepare a mixed solution;
s2, adding 6kg of sodium carbonate solution with the mass concentration of 15% into the mixed solution, wherein the adding speed of the sodium carbonate solution is controlled to be 2.5L/min, and obtaining coprecipitated starch;
s3, washing the coprecipitated starch body by adopting water until the pH value of the washed water is within the range of 6.5-7.5, and stopping washing;
s4, drying the washed coprecipitated starch body for the first time to constant weight, wherein the temperature of the primary drying is 110 ℃, and calcining the coprecipitated starch body after the weight of the coprecipitated starch body is constant weight, wherein the calcining temperature is 700 ℃ and the time is 6 hours;
s5, performing primary wet grinding on the calcined coprecipitated starch, controlling the rotating speed of the primary wet grinding to be 85r/min, controlling the wet grinding time to be 1.2h, and then performing secondary drying on the coprecipitated starch after the wet grinding to constant weight, wherein the secondary drying temperature is 110 ℃, so as to obtain the silver oxide doped with amphoteric oxide;
s6, coating 100kgSilver tin oxide base powder AgSnO prepared by the method 2 Mixing with 0.6kg silver oxide doped with amphoteric oxide, performing secondary wet milling, controlling the rotation speed of the secondary wet milling to be 85r/min, controlling the wet milling time to be 1.2h, and then drying to constant weight at the drying temperature of 110 ℃ to obtain the modified silver tin oxide.
[ example 2 ]
A preparation process of modified silver tin oxide comprises the following steps:
s1, uniformly stirring 2.8kg of copper nitrate solution with the mass concentration of 25% and 4.4kg of silver nitrate solution with the mass concentration of 25% to prepare a mixed solution;
s2, adding 6kg of sodium carbonate solution with the mass concentration of 15% into the mixed solution, wherein the adding speed of the sodium carbonate solution is controlled to be 2.5L/min, and obtaining coprecipitated starch;
s3, washing the coprecipitated starch body by adopting water until the pH value of the washed water is within the range of 6.5-7.5, and stopping washing;
s4, drying the washed coprecipitated starch body for the first time to constant weight, wherein the temperature of the primary drying is 110 ℃, and calcining the coprecipitated starch body after the weight of the coprecipitated starch body is constant weight, wherein the calcining temperature is 700 ℃ and the time is 6 hours;
s5, performing primary wet grinding on the calcined coprecipitated starch, controlling the rotating speed of the primary wet grinding to be 85r/min, controlling the wet grinding time to be 1.2h, and then performing secondary drying on the coprecipitated starch after the wet grinding to constant weight, wherein the secondary drying temperature is 110 ℃, so as to obtain the silver oxide doped with amphoteric oxide;
s6, preparing silver tin oxide base powder AgSnO by using 100kg coating method 2 Mixing with 0.6kg silver oxide doped with amphoteric oxide, performing secondary wet milling, controlling the rotation speed of the secondary wet milling to be 85r/min, controlling the wet milling time to be 1.2h, and then drying to constant weight at the drying temperature of 110 ℃ to obtain the modified silver tin oxide.
Comparative example
Comparative example 1
The preparation process of the modified silver tin oxide base powder comprises the following steps:
silver tin oxide base powder AgSnO prepared by coating 100kg 2 Uniformly mixing with 0.6kg zinc oxide powder, performing wet grinding at a rotating speed of 85r/min for 1.2h, and drying to constant weight at 110 ℃ to obtain the modified silver tin oxide.
Performance test
Preparing a sample to be tested:
the modified tin oxides prepared in examples 1-2 and comparative example 1 were prepared into electrical contact materials according to conventional processes, respectively, and then the electrical contact materials were subjected to physical properties and electrical properties.
The preparation process of the electrical contact material comprises the following steps:
annealing: heating the modified silver tin oxide to 500 ℃, preserving heat for 3 hours, and then cooling to 25 ℃ to obtain annealed powder;
and (3) forming: molding the annealed powder under the pressure of 300MPa, and sintering at 800 ℃ for 3 hours to obtain an ingot blank;
extruding: and (3) carrying out hot extrusion on the ingot blank at 800 ℃ to obtain the electrical contact material, wherein the extrusion ratio is 300.
1. Tensile strength: the test is carried out by referring to GB/T228.1-2021 tensile test of metal materials, and the unit is MPa.
2. Volume resistivity: the test is carried out by referring to section 5 in the hardness test of GB/T5586-2016 electric contact material basic Performance test method, and the unit is mu omega cm.
3. Electrical life: the electrical contact material is processed into rivet type electrical contacts with the size phi of 2.0 to 1.5, and the test results on a simulation tester are used for simulating the test conditions: the current is 30A, the voltage is 250V, the current is switched on for 1s and off for 1s, and the breaking force is 18g.
Table 1 electrical contact material performance test
As can be seen from the combination of the electrical contact material 1 and the electrical contact material 3 and the data in table 1, when zinc oxide powder is directly used to replace silver oxide doped with amphoteric oxide and silver tin oxide base powder to prepare modified silver tin oxide, the tensile strength and the electrical life of the electrical contact material prepared from the modified silver tin oxide are obviously reduced, because: the zinc oxide powder has poor dispersibility in the silver tin oxide base powder.
The present embodiment is merely illustrative of the present application and is not limiting of the present application, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as necessary, but are protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. A preparation process of modified silver tin oxide is characterized in that: the method comprises the following steps:
uniformly stirring a salt crystal solution of the amphoteric oxide and a silver nitrate crystal solution to prepare a mixed solution;
adding carbonate solution into the mixed solution to prepare coprecipitated starch; the mass concentration of the carbonate solution is 15-20%, and the adding speed of the carbonate solution is controlled to be 2-3L/min;
washing, primary drying, calcining, primary wet grinding and secondary drying are sequentially carried out on the coprecipitated starch body, so that silver oxide doped with amphoteric oxide is obtained; the calcination conditions of the coprecipitated starch are as follows: the calcination temperature is 680-720 ℃ and the calcination time is 5-7h;
mixing the silver tin oxide base powder prepared by the coating method with silver oxide doped with amphoteric oxide, performing secondary wet grinding, and then drying to obtain the modified silver tin oxide.
2. The process for preparing modified silver tin oxide according to claim 1, wherein: the weight ratio of carbonate in the carbonate solution to silver nitrate in the silver nitrate crystal solution is (0.8-1.2): 1.
3. the process for preparing modified silver tin oxide according to claim 1, wherein: the temperature of the primary drying is controlled to be 100-120 ℃.
4. The process for preparing modified silver tin oxide according to claim 1, wherein: the rotating speed of the primary wet grinding is 80-90r/min, and the wet grinding time is 1-1.5h.
5. The process for preparing modified silver tin oxide according to claim 1, wherein: the temperature of the secondary drying is controlled to be 100-120 ℃.
6. The process for preparing modified silver tin oxide according to claim 1, wherein: the weight ratio of the silver tin oxide base powder to the silver oxide doped with the amphoteric oxide is 1: (0.006-0.02).
7. The process for preparing modified silver tin oxide according to claim 1, wherein: the rotating speed of the secondary wet grinding is 80-90r/min, and the wet grinding time is 1-1.5h.
8. A modified silver tin oxide, characterized by: is prepared by the preparation process of the modified silver tin oxide according to any one of claims 1 to 7.
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