CN110468295B - Strong interface combination type Ag/SnO2Preparation method of electric contact material - Google Patents
Strong interface combination type Ag/SnO2Preparation method of electric contact material Download PDFInfo
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- CN110468295B CN110468295B CN201910715907.9A CN201910715907A CN110468295B CN 110468295 B CN110468295 B CN 110468295B CN 201910715907 A CN201910715907 A CN 201910715907A CN 110468295 B CN110468295 B CN 110468295B
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- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
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- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
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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
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- 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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- 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
Abstract
The invention relates to a strong interface combination type Ag/SnO2A preparation method of an electric contact material belongs to the technical field of electric contact materials. The invention adopts the composite aerogel material to modify the whole material structure, and SnO is adopted2The N-type wide bandgap semiconductor is a typical N-type wide bandgap semiconductor, in a composite material, the number of oxygen vacancies is large in aerogel framework particles, the main existing form of nanocrystals is SnO, meanwhile, in SnO2 aerogel with high surface area and extremely small grain size, surface atoms account for most, the material is mainly composed of surfaces and greatly differs from a common bulk material, the electronic structure of the framework particles is similar to the surface of the bulk material, the material with excellent structural performance is a modified matrix through the aerogel, and the aerogel is a nano porous three-dimensional network structure material formed by aggregation of nano-scale colloidal particles or high polymer molecules, so that the performance of interface bonding between materials is effectively improved, and the bonding strength of the materials is further improved.
Description
Technical Field
The invention relates to a strong interface combination type Ag/SnO2A preparation method of an electric contact material belongs to the technical field of electric contact materials.
Background
Electrical contacts are defined as interfaces between current-carrying elements of electrical and electronic equipment, and components containing such interfaces, with the aim of ensuring continuity of the electrical circuit. The electric contact material is a core component and a key material of electric appliances (such as switches, starters, relays, instruments and meters) for on-off control and load current in electric power preparation and electric appliance circuits, and mainly bears the functions of on-off, current guiding and current isolation. The performance of the electronic device directly influences the reliability, stability, accuracy and service life of the electronic device. Therefore, the electric contact material is not only the heart of the electronic and electric products, but also the lethal point of the electronic and electric products.
In the practical application process, the following performance requirements are provided for the ideal electric contact material:
(1) physical properties: the low resistivity is to guarantee the good electric conductance, the low steam pressure is to limit the metal steam density after the arc-starting, the high thermal conductivity is convenient to make the heat that the electric arc or joule heat source produced transport to the contact base as soon as possible and disperse, high melting point, boiling point, latent heat of decomposition and specific heat are in order to reduce the tendency of arcing, in addition, the electron work function is high, in order to guarantee that the arc-starting voltage is high.
(2) Chemical properties: the electrical contact material should have relatively high chemical stability, i.e. high electrochemical potential. Oxidation, carbonization, vulcanization and other compound film layers which are not easily conductive are not formed in the air, and even if formed, they should be easily decomposed.
(3) Electrical contact performance: the method is summarized into three points, low and stable contact resistance, good fusion welding resistance and arc erosion resistance.
(4) Mechanical properties: suitable hardness and modulus of elasticity. The lower hardness can increase the contact area when the contact pressure is constant, reduce the contact resistance, and reduce the contact heating, the static melting tendency and the moving contact bounce; the higher hardness can reduce the welding area and improve the mechanical abrasion capability. In addition, the electric contact material is required to be easily soldered at room temperature and to maintain a certain strength, toughness, etc. at high temperatures.
Various methods have been developed for the preparation of electrical fusion materials, and are described in two categories below. One is the mainstream process in industrial production, and there are four common processes: general powder metallurgy, infiltration, alloy internal oxidation and powder pre-oxidation; the other is the leading-edge technology developed by a few enterprises or research institutions, such as isostatic pressing, ultrasonic pressing, electric arc melting, ion implantation, reaction synthesis, indirect repeated extrusion, fiber reinforcement and the like, and is the hot spot of the current research.
The powder metallurgy method is widely applied to preparing various electric contact materials, such as Ag/SnO2Ag/ZnO, Ag/Ni, Ag/C, etc. The technological process includes compounding silver powder and reinforcing phase powder in certain proportion, mixing, pressing to form, sintering, rolling into plate or extruding into wire to produce various electric contact elements. The powder metallurgy method has the advantages that the method is suitable for preparing electric contact materials with any components, the tissue structure of the materials is easy to adjust, the 'poor metal oxide area' is eliminated, and meanwhile, the method is simple in process, low in cost and low in investment, so that the method is mainly used for preparing bodiesLarge volume and simple shape. The defects are that the hardness and density of the electric contact material prepared by the powder metallurgy method are generally lower than those of the electric contact material prepared by the internal oxidation method, the porosity of the material is high, oxide particles are coarse, and the problems of large contact resistance, high temperature rise and the like are easily caused. In addition, if defects of uneven powder mixing, nano-particle agglomeration and the like occur in the traditional process, the comprehensive performance of the electric contact material can be seriously influenced.
The infiltration method is commonly used for preparing electric contact materials of Cu/W, Cu/Cr, Ag/W, Cu/Mo and other systems, and is characterized by specially aiming at the preparation of electric contact materials of refractory metals and low-melting-point metal pseudo alloys. The infiltration method is divided into two methods, one method is that refractory metals (W, Mo, Cr and the like) are sintered into a framework at high temperature, and then the molten Ag or Cu is infiltrated into the framework under the action of capillary force at low temperature or in a reducing atmosphere; and the other method is to sinter part of the mixed powder at low temperature and then infiltrate the low-melting-point metal to prepare the required composite electric contact material.
The alloy internal oxidation method is an important means for preparing Ag/MeO electric contact composite materials. Firstly, Ag and other metal components are smelted into an alloy ingot according to a ratio, then rolling and punch forming are carried out, and finally internal oxidation treatment is carried out, so that the Ag is not easily oxidized at a high temperature, and the Ag/MeO composite material consisting of the silver and the metal oxide is formed after the non-noble metal components are fully oxidized.
The alloy powder pre-oxidation method starts from the atomized alloy powder which is rapidly solidified, so that the period of internal oxidation is greatly reduced, the mass points of oxides are uniformly and finely distributed, and the material has better fusion welding resistance and arc erosion resistance. Meanwhile, each oxide particle in the material is connected with the Ag-rich phase, so that the density of Ag-Ag conductive channels in the material is increased, and the resistivity of the material is reduced. However, the density and the mechanical and physical properties of the material obtained by the method are not as high as those of the electric contact material prepared by internal oxidation, and the method is a preparation method of the electric contact material with relatively balanced advantages and disadvantages in the aspects of process period and cost.
Ag-based electrical contact materials are the most widely used materials in the electrical contact industry, wherein Ag/CdO electrical contacts account for more than 60% of all electrical contact products. In place of Ag/CdOIn an environment-friendly electrical contact material system, Ag/SnO2Is the most studied one, but SnO2Physical properties of the compounds per se have some disadvantages, e.g. SnO2The resistivity of (a) is too large, exceeding the resistivity of the electrical contact material by 8 orders of magnitude; SnO2The interface compatibility of the particles and Ag is poor, and segregation is easy to generate; has the problems of high contact temperature, poor arc erosion resistance and the like. The scientific research worker adopts a plurality of methods to carry out the treatment on Ag/SnO2The material is modified, and favorable progress is achieved. On the other hand, a part of research is focused on exploring a new electric contact material system, and particularly research on Ag/conductive ceramic electric contact materials provides a new idea for developing environment-friendly electric contact materials.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem of poor contact resistance of the existing material, a preparation method of a strong interface combination type Ag/SnO2 electric contact material is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) respectively weighing 45-50 parts by weight of acetonitrile, 35-40 parts by weight of ethyl orthosilicate, 3-5 parts by weight of deionized water and 6-8 parts by weight of propylene oxide, placing the materials in a triangular flask, stirring and mixing the materials, and standing the mixture at room temperature for 1-2 hours to obtain a matrix liquid A; respectively weighing 45-50 parts by weight of acetonitrile, 3-5 parts by weight of copper chloride dihydrate and 6-8 parts by weight of deionized water, placing the materials in a beaker, stirring and mixing the materials, and placing the mixture at room temperature for standing for 1-2 hours to obtain a matrix solution B;
(2) respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 10-15 parts by weight of acetic acid solution and 10-15 parts by weight of butyl titanate in a triangular flask, and stirring and mixing to obtain a modified composite liquid; stirring and mixing the matrix liquid B, the matrix liquid A and the modified complex liquid according to the volume ratio of 1: 2 to obtain a mixed liquid, then dropwise adding the mixed liquid into propylene oxide according to the mass ratio of 1: 5, collecting the dropwise added complex liquid after the dropwise addition is finished, placing the dropwise added complex liquid into a heat preservation reaction, and collecting a reaction sol liquid;
(3) respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 3-5 parts by weight of stannic chloride and 10-15 parts by weight of propylene oxide, and placing the materials in a triangular furnaceStirring and mixing in a bottle, standing at room temperature, collecting the aged gel solution, stirring and mixing the aged gel solution and the reaction sol solution, performing ultrasonic dispersion, standing at room temperature for aging, washing, and performing CO treatment2Drying in a supercritical fluid drying device, collecting dry aerogel after drying is finished, heating and preserving heat for reaction, standing and cooling to room temperature, ball-milling and sieving to obtain composite tin oxide aerogel powder;
(4) taking silver powder, carrying out ball milling and sieving, taking sieved powder, mixing the powder with the sieved powder according to the mass ratio of 1: 8, stirring and mixing the composite tin oxide aerogel powder and the sieved powder, placing the mixture in a high-energy ball mill, carrying out ball milling, collecting ball-milled mixed powder, carrying out compression molding, collecting a pressed blank, placing the pressed blank in a muffle furnace, carrying out heating and heat-preservation sintering, carrying out re-pressing treatment, carrying out secondary heating and heat-preservation sintering, and carrying out annealing treatment to obtain the strong interface bonding type Ag/SnO2An electrical contact material.
The concentration of the acetic acid solution is 1 percent by mass.
And the washing treatment is to sequentially and respectively wash the water-free ethanol and the acetone for 3-5 times.
Said CO2The drying parameters of the supercritical fluid drying device are that the critical temperature is controlled to be 31-32 ℃, and the pressure is 7.0-7.5 MPa.
The acceleration rate of the mixed liquid drops is 0.1 mL/s.
The aperture of the screen mesh is 70-75 mu m.
The compound ratio of the aging gel liquid to the reaction sol liquid is 1: 1 according to the mass ratio.
The repressing pressure intensity is 1250-1300 MPa.
The secondary heating and heat preservation sintering is to heat up to 655-680 ℃ at the speed of 5 ℃/min, and to preserve heat and sinter for 3-4 h.
The high-energy ball mill is preferably a QM-3A type high-energy ball mill.
Compared with other methods, the method has the beneficial technical effects that:
(1) the technical scheme of the invention is to dope the composite titanium oxide/silicon oxide aerogel material prepared by the invention with copper oxideThe composite nano tin oxide aerogel is prepared, the effective addition of copper oxide effectively improves the adhesion work of the composite material, and the adhesion work of the material represents the wettability of the material, because according to thermodynamic analysis, the wetting process is determined by the adhesion work which represents the work consumed by separating a unit solid-liquid interface and is used for measuring the bonding strength of solid and liquid, the larger the adhesion work is, the firmer the solid-liquid interface is bonded, the more stable the system is, and simultaneously, the copper oxide effectively changes the components of a reinforcement body to reduce the solid-liquid interface tension, so that the wettability can be obviously improved, and the Ag/SnO can ensure that the Ag/SnO has better wettability2The interface is changed from mechanical combination into dissolution and wetting combination, and the interaction of atom (molecule) layers occurs, so that the bonding strength of the interface can be improved, and simultaneously, the addition of the copper oxide material can obviously inhibit SnO2The particles are aggregated and grown at high temperature, and the nano SnO containing doping elements2The particles are dispersed and distributed in the equivalent Ag, so that the viscosity of the Ag at high temperature can be further increased, the solidification time of an Ag melting layer is greatly reduced, the surface layer structure is greatly refined and homogenized, the probability of forming particles on the surface of the contact is obviously reduced due to the uniformly refined surface layer structure, and the breakdown weakness is reduced, thereby being beneficial to improving the voltage resistance and the arc erosion resistance of the alloy;
(2) the technical scheme of the invention adopts the composite aerogel material to modify the whole material structure, and SnO is used for modifying2The N-type wide bandgap semiconductor is a typical N-type wide bandgap semiconductor, in a composite material, the number of oxygen vacancies is large in aerogel framework particles, the main existing form of nanocrystals is SnO, meanwhile, in SnO2 aerogel with high surface area and extremely small grain size, surface atoms account for most, the material is mainly composed of surfaces and greatly differs from a common bulk material, the electronic structure of the framework particles is similar to the surface of the bulk material, the material with excellent structural performance is a modified matrix through the aerogel, and the aerogel is a nano porous three-dimensional network structure material formed by aggregation of nano-scale colloidal particles or high polymer molecules, so that the performance of interface bonding between materials is effectively improved, and the bonding strength of the materials is further improved.
Detailed Description
Respectively weighing 45-50 parts by weight of acetonitrile, 35-40 parts by weight of ethyl orthosilicate, 3-5 parts by weight of deionized water and 6-8 parts by weight of propylene oxide, placing the materials in a triangular flask, stirring and mixing the materials, and standing the mixture at room temperature for 1-2 hours to obtain a matrix liquid A; respectively weighing 45-50 parts by weight of acetonitrile, 3-5 parts by weight of copper chloride dihydrate and 6-8 parts by weight of deionized water, placing the materials in a beaker, stirring and mixing the materials, and placing the mixture at room temperature for standing for 1-2 hours to obtain a matrix solution B; respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 10-15 parts by weight of 1% acetic acid solution and 10-15 parts by weight of butyl titanate in a triangular flask, and stirring and mixing to obtain a modified composite liquid; stirring and mixing the matrix liquid B, the matrix liquid A and the modified complex liquid according to the volume ratio of 1: 2 to obtain a mixed liquid, then dropwise adding the mixed liquid into propylene oxide according to the mass ratio of 1: 5, controlling the dropwise adding speed to be 0.1mL/s, after the dropwise adding is finished, collecting the dropwise added complex liquid, placing the dropwise added complex liquid at the temperature of 30-40 ℃ for heat preservation reaction for 25-30 min, and collecting a reaction sol liquid; respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 3-5 parts by weight of tin chloride and 10-15 parts by weight of propylene oxide in a triangular flask, stirring and mixing, standing at room temperature for 3-5 hours, collecting an aging gel liquid, stirring and mixing the aging gel liquid and a reaction sol liquid according to the mass ratio of 1: 1, performing ultrasonic dispersion for 10-15 minutes under 200-300W, standing and aging at room temperature for 40-48 hours, sequentially washing with absolute ethyl alcohol and acetone for 3-5 times, and then performing CO (carbon monoxide) reaction2Drying in a supercritical fluid drying device, controlling the critical temperature to be 31-32 ℃ and the pressure to be 7.0-7.5 MPa, after drying, collecting dried aerogel, placing the dried aerogel in a muffle furnace at 100-110 ℃, heating to 455-480 ℃ at 1 ℃/min, carrying out heat preservation reaction for 3-5 h, standing, cooling to room temperature, placing at 250-300 r/min, carrying out ball milling for 3-5 h, and sieving with a 500-mesh sieve to obtain composite tin oxide aerogel powder; taking silver powder, carrying out ball milling and sieving, setting the aperture of a sieve to be 70-75 mu m, taking sieved powder, mixing the powder and the sieved powder according to the mass ratio of 1: 8, stirring and mixing the powder and the sieved powder, placing the mixture in a high-energy ball mill, carrying out ball milling for 1h in the environment that the ball milling medium is a steel ball and the mass ratio of ball material is 10: 1, collecting ball-milled mixed powder, placing the ball-milled mixed powder in a press molding under 250-300 MPa, collecting the press moldingPlacing the blank in a muffle furnace at 100-110 ℃, heating to 655-680 ℃ at 5 ℃/min, carrying out heat preservation sintering for 6-8 h, carrying out repressing treatment at 1250-1300 MPa, then placing in the muffle furnace at 100-110 ℃, heating to 655-680 ℃ at 5 ℃/min, carrying out heat preservation sintering for 3-4 h, and carrying out annealing treatment at 250-280 ℃ for 2-3 h to obtain the strong interface bonding type Ag/SnO2An electrical contact material; the high-energy ball mill is preferably a QM-3A type high-energy ball mill.
Example 1
Respectively weighing 45 parts of acetonitrile, 35 parts of ethyl orthosilicate, 3 parts of deionized water and 6 parts of epoxypropane in parts by weight, placing the materials in a triangular flask, stirring and mixing the materials, and placing the mixture at room temperature for standing for 1 hour to obtain a matrix solution A; respectively weighing 45 parts of acetonitrile, 3 parts of copper chloride dihydrate and 6 parts of deionized water in parts by weight, placing the materials in a beaker, stirring and mixing the materials, placing the mixture at room temperature and standing the mixture for 1 hour to obtain a matrix solution B; respectively weighing 45 parts by weight of absolute ethyl alcohol, 10 parts by weight of 1% acetic acid solution and 10 parts by weight of butyl titanate in a triangular flask, and stirring and mixing to obtain a modified composite liquid; stirring and mixing the matrix liquid B, the matrix liquid A and the modified complex liquid according to the volume ratio of 1: 2 to obtain a mixed liquid, then dropwise adding the mixed liquid into propylene oxide according to the mass ratio of 1: 5, controlling the dropwise adding speed to be 0.1mL/s, after the dropwise adding is finished, collecting the dropwise added complex liquid, placing the dropwise added complex liquid at the temperature of 30 ℃ for heat preservation and reaction for 25min, and collecting a reaction sol liquid; respectively weighing 45 parts by weight of absolute ethyl alcohol, 3 parts by weight of tin chloride and 10 parts by weight of propylene oxide, placing the materials into a triangular flask, stirring and mixing the materials, placing the materials at room temperature for standing for 3 hours, collecting an aging gel liquid, stirring and mixing the aging gel liquid and a reaction sol liquid according to the mass ratio of 1: 1, placing the mixture under 200-300W for ultrasonic dispersion for 10 minutes, then placing the mixture at room temperature for aging for 40 hours, sequentially washing the mixture for 3 times by using absolute ethyl alcohol and acetone, and then performing CO (carbon monoxide) reaction2Drying in a supercritical fluid drying device, controlling the critical temperature to be 31 ℃ and the pressure to be 7.0MPa, collecting dried aerogel after drying, placing the dried aerogel in a muffle furnace at 100 ℃, heating to 455 ℃ at the rate of 1 ℃/min, keeping the temperature for reaction for 3h, standing, cooling to room temperature, placing the mixture in a ball mill at the speed of 250r/min for 3h, and sieving the mixture with a 500-mesh sieve to obtain composite tin oxide aerogel powder; taking silver powder, carrying out ball milling and sieving,setting the aperture of a sieve mesh to be 70 mu m, taking the sieved powder, mixing the powder and the sieved powder according to the mass ratio of 1: 8, stirring and mixing the powder and the sieved powder, placing the mixture in a QM-3A type high-energy ball mill, ball milling for 1h under the environment that the ball milling medium is a steel ball and the ball material mass ratio is 10: 1, collecting the ball-milled mixed powder, placing the ball-milled mixed powder under 250MPa for press forming, collecting a pressed blank, placing the pressed blank in a muffle furnace at 100 ℃, heating to 655 ℃ at 5 ℃/min, carrying out heat preservation sintering for 6h, carrying out repressing treatment at 1250MPa, then placing the pressed blank in the muffle furnace at 100 ℃, heating to 655 ℃ at 5 ℃/min, carrying out heat preservation sintering for 3h, and carrying out annealing treatment at 250 ℃ for 2h to obtain the strong interface bonding type Ag2An electrical contact material.
Example 2
Respectively weighing 47 parts of acetonitrile, 37 parts of ethyl orthosilicate, 4 parts of deionized water and 7 parts of epoxypropane in parts by weight, placing the materials in a triangular flask, stirring and mixing the materials, and standing the mixture at room temperature for 1 hour to obtain a matrix solution A; respectively weighing 47 parts by weight of acetonitrile, 4 parts by weight of copper chloride dihydrate and 7 parts by weight of deionized water, placing the materials in a beaker, stirring and mixing the materials, and placing the mixture at room temperature for standing for 1 hour to obtain a matrix solution B; respectively weighing 47 parts by weight of absolute ethyl alcohol, 12 parts by weight of 1% acetic acid solution and 12 parts by weight of butyl titanate, placing the materials in a triangular flask, and stirring and mixing to obtain a modified composite liquid; stirring and mixing the matrix liquid B, the matrix liquid A and the modified complex liquid according to the volume ratio of 1: 2 to obtain a mixed liquid, then dropwise adding the mixed liquid into propylene oxide according to the mass ratio of 1: 5, controlling the dropwise adding speed to be 0.1mL/s, after the dropwise adding is finished, collecting the dropwise added complex liquid, placing the dropwise added complex liquid at 35 ℃ for heat preservation and reaction for 28min, and collecting a reaction sol liquid; respectively weighing 47 parts by weight of absolute ethyl alcohol, 4 parts by weight of stannic chloride and 12 parts by weight of propylene oxide, placing the materials into a triangular flask, stirring and mixing the materials, placing the materials at room temperature for standing for 4 hours, collecting an aging gel liquid, stirring and mixing the aging gel liquid and a reaction sol liquid according to the mass ratio of 1: 1, placing the mixture under 250W for ultrasonic dispersion for 12 minutes, then placing the mixture at room temperature for aging for 44 hours, sequentially and respectively washing the mixture for 4 times by using absolute ethyl alcohol and acetone, and then performing CO (carbon monoxide) reaction2Drying in supercritical fluid drying device at critical temperature of 31 deg.C and pressure of 7.2MPa, collecting dried aerogel and placing at 105 deg.C after dryingHeating to 465 ℃ at the speed of 1 ℃/min in a muffle furnace, carrying out heat preservation reaction for 4 hours, standing, cooling to room temperature, ball-milling at the speed of 280r/min for 4 hours, and sieving with a 500-mesh sieve to obtain composite tin oxide aerogel powder; taking silver powder, carrying out ball milling and sieving, setting the aperture of a sieve to be 72 mu m, taking sieved powder, carrying out ball milling for 1h in an environment with the mass ratio of steel balls to ball materials being 10: 1 according to the mass ratio of 1: 8 of the sieved powder to the composite tin oxide aerogel powder, stirring and mixing the composite tin oxide aerogel powder and the sieved powder, placing the mixture in a QM-3A type high-energy ball mill, collecting the ball-milled mixed powder, placing the ball-milled mixed powder in a 280MPa press molding, collecting a pressed blank, placing the pressed blank in a 105 ℃ muffle furnace, heating to 665 ℃ according to the temperature of 5 ℃/min, carrying out heat preservation and sintering for 7h, carrying out re-pressing treatment under the pressure of 1275MPa, then placing the pressed blank in the 105 ℃ muffle furnace, heating to 665 ℃ according to the temperature of 5 ℃/min, carrying out heat preservation and sintering for 32An electrical contact material.
Example 3
Respectively weighing 50 parts of acetonitrile, 40 parts of ethyl orthosilicate, 5 parts of deionized water and 8 parts of epoxypropane in parts by weight, placing the materials in a triangular flask, stirring and mixing the materials, placing the mixture at room temperature and standing the mixture for 2 hours to obtain a matrix solution A; respectively weighing 50 parts of acetonitrile, 5 parts of copper chloride dihydrate and 8 parts of deionized water according to parts by weight, placing the materials in a beaker, stirring and mixing the materials, placing the mixture at room temperature and standing the mixture for 2 hours to obtain a matrix solution B; respectively weighing 50 parts by weight of absolute ethyl alcohol, 15 parts by weight of 1% acetic acid solution and 15 parts by weight of butyl titanate in a triangular flask, and stirring and mixing to obtain a modified composite liquid; stirring and mixing the matrix liquid B, the matrix liquid A and the modified complex liquid according to the volume ratio of 1: 2 to obtain a mixed liquid, then dropwise adding the mixed liquid into propylene oxide according to the mass ratio of 1: 5, controlling the dropwise adding speed to be 0.1mL/s, after the dropwise adding is finished, collecting the dropwise added complex liquid, placing the dropwise added complex liquid at 40 ℃ for heat preservation and reaction for 30min, and collecting a reaction sol liquid; respectively weighing 50 parts by weight of absolute ethyl alcohol, 5 parts by weight of stannic chloride and 15 parts by weight of propylene oxide, placing the materials into a triangular flask, stirring and mixing the materials, placing the materials at room temperature for standing for 5 hours, collecting an aging gel liquid, stirring and mixing the aging gel liquid and a reaction sol liquid according to the mass ratio of 1: 1, placing the mixture under 300W for ultrasonic dispersion for 15 minutes, then placing the mixture at room temperature for aging for 48 hours, and using absolute ethyl alcohol and propylene glycolWashing ketone for 5 times, and then washing with CO2Drying in a supercritical fluid drying device, controlling the critical temperature to be 32 ℃ and the pressure to be 7.5MPa, collecting dried aerogel after drying, placing the dried aerogel in a muffle furnace at 110 ℃, heating to 480 ℃ at the speed of 1 ℃/min, preserving heat, reacting for 5 hours, standing, cooling to room temperature, placing at 300r/min, ball-milling for 5 hours, and sieving with a 500-mesh sieve to obtain composite tin oxide aerogel powder; taking silver powder, carrying out ball milling and sieving, setting the aperture of a sieve to be 75 mu m, taking sieved powder, carrying out ball milling for 1h in an environment that the mass ratio of a ball milling medium to a ball material is 10: 1 according to the mass ratio of 1: 8, stirring and mixing the composite tin oxide aerogel powder and the sieved powder, placing the mixture in a QM-3A type high-energy ball mill, collecting the ball-milled mixed powder, placing the ball-milled mixed powder in a 300MPa press forming machine, collecting a pressed blank, placing the pressed blank in a 110 ℃ muffle furnace, heating to 680 ℃ according to the speed of 5 ℃/min, carrying out heat preservation and sintering for 8h, carrying out re-pressing treatment at 1300MPa, then placing the pressed blank in the 110 ℃ muffle furnace, heating to 680 ℃ according to the speed of 5 ℃/min, carrying out heat preservation and sintering for 4h, and carrying out annealing treatment for 3h2An electrical contact material.
Comparative example: an electrical contact material manufactured by Dongguan company.
The electric contact materials prepared in the examples and the comparative examples are detected, and the specific detection is as follows:
hardness: the apparatus used was a Blowev hardness tester model HBRVU-187.5, the indenter was a regular square pyramid made of diamond, the angle between the two opposite faces was 136 °, the test force was 294.2N, and the holding time was 15 s.
Resistivity: measuring the square resistance of a sample by using an RTS-8 type four-probe tester, and then converting the square resistance into a conductivity value; the resistivity of the sheet was measured with a D60K digital metal conductivity meter.
Electrical contact performance: the JF04C type electrical life simulation tester produced by Kunming noble research King-peak science and technology Limited company is adopted to represent the electrical life and the dynamic electrical contact performance of an electrical contact sample, and the experimental conditions are that the alternating current load voltage is 380V, the load current is 25A, and the test frequency is 60 times/min. The samples were subjected to over 10,000 on-off cycling tests.
The specific test results are shown in table 1.
Table 1 comparative table of property characterization
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| hardness/HV | 88.09 | 88.56 | 89.01 | 70.13 |
| Resistivity/u Ω · cm | 2.81 | 2.76 | 2.93 | 3.73 |
| Contact resistance/m omega | 4.41 | 4.30 | 4.22 | 9.31 |
As can be seen from Table 1, the electrical contact material prepared by the present invention has good hardness and electrical contact properties.
Claims (9)
1. Strong interface combination type Ag/SnO2The preparation method of the electric contact material is characterized by comprising the following specific preparation steps:
(1) respectively weighing 45-50 parts by weight of acetonitrile, 35-40 parts by weight of ethyl orthosilicate, 3-5 parts by weight of deionized water and 6-8 parts by weight of propylene oxide, placing the materials in a triangular flask, stirring and mixing the materials, and standing the mixture at room temperature for 1-2 hours to obtain a matrix liquid A; respectively weighing 45-50 parts by weight of acetonitrile, 3-5 parts by weight of copper chloride dihydrate and 6-8 parts by weight of deionized water, placing the materials in a beaker, stirring and mixing the materials, and placing the mixture at room temperature for standing for 1-2 hours to obtain a matrix solution B;
(2) respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 10-15 parts by weight of acetic acid solution and 10-15 parts by weight of butyl titanate in a triangular flask, and stirring and mixing to obtain a modified composite liquid; stirring and mixing the matrix liquid B, the matrix liquid A and the modified complex liquid according to the volume ratio of 1: 2 to obtain a mixed liquid, then dropwise adding the mixed liquid into propylene oxide according to the mass ratio of 1: 5, collecting the dropwise added complex liquid after the dropwise addition is finished, placing the dropwise added complex liquid into a heat preservation reaction, and collecting a reaction sol liquid;
(3) respectively weighing 45-50 parts by weight of absolute ethyl alcohol, 3-5 parts by weight of stannic chloride and 10-15 parts by weight of propylene oxide in a triangular flask, stirring and mixing, standing at room temperature, collecting an aged gel liquid, stirring and mixing the aged gel liquid and a reaction sol liquid, performing ultrasonic dispersion, standing at room temperature for aging, washing, and performing CO (carbon monoxide) treatment2Drying in a supercritical fluid drying device, collecting dry aerogel after drying is finished, heating and preserving heat for reaction, standing and cooling to room temperature, ball-milling and sieving to obtain composite tin oxide aerogel powder;
(4) taking silver powder, carrying out ball milling and sieving, setting the aperture of a sieve to be 70-75 mu m, taking sieved powder, mixing the powder and the sieved powder according to the mass ratio of 1: 8, stirring and mixing the composite tin oxide aerogel powder and the sieved powder, placing the mixture in a high-energy ball mill, carrying out ball milling, collecting ball-milled mixed powder, carrying out compression molding, collecting a compression blank, placing the compression blank in a muffle furnace, heating, carrying out heat preservation and sintering, carrying out re-compression treatment, carrying out secondary heating, carrying out heat preservation and sintering, and carrying out annealing treatment to obtain the strong interface combination type Ag/SnO2An electrical contact material.
2. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: the concentration of the acetic acid solution is 1 percent by mass.
3. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: the washing treatment is to use absolute ethyl alcoholAnd sequentially washing with acetone for 3-5 times respectively.
4. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: said CO2The drying parameters of the supercritical fluid drying device are that the critical temperature is controlled to be 31-32 ℃, and the pressure is 7.0-7.5 MPa.
5. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: the acceleration rate of the mixed liquid drops is 0.1 mL/s.
6. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: the compound ratio of the aging gel liquid to the reaction sol liquid is 1: 1 according to the mass ratio.
7. The method for preparing the Ag/SnO2 electric contact material with strong interface bonding property according to claim 1, wherein the method comprises the following steps: the repressing pressure intensity is 1250-1300 MPa.
8. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: the secondary heating and heat preservation sintering is to heat up to 655-680 ℃ at the speed of 5 ℃/min, and to preserve heat and sinter for 3-4 h.
9. A strong interface bonding type Ag/SnO according to claim 12The preparation method of the electric contact material is characterized by comprising the following steps: the high-energy ball mill is preferably a QM-3A type high-energy ball mill.
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