CN112375931A - Preparation method of tetrapod-like whisker reinforced silver zinc oxide contact material - Google Patents
Preparation method of tetrapod-like whisker reinforced silver zinc oxide contact material Download PDFInfo
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- CN112375931A CN112375931A CN202011118336.XA CN202011118336A CN112375931A CN 112375931 A CN112375931 A CN 112375931A CN 202011118336 A CN202011118336 A CN 202011118336A CN 112375931 A CN112375931 A CN 112375931A
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- zinc oxide
- tetrapod
- silver
- whisker reinforced
- contact material
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- 239000000463 material Substances 0.000 title claims abstract description 61
- DUCFBDUJLLKKPR-UHFFFAOYSA-N [O--].[Zn++].[Ag+] Chemical compound [O--].[Zn++].[Ag+] DUCFBDUJLLKKPR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000011787 zinc oxide Substances 0.000 claims abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920003081 Povidone K 30 Polymers 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 25
- 239000004332 silver Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 20
- 239000001119 stannous chloride Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 67
- 238000000227 grinding Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- 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
- 238000007664 blowing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- 230000007547 defect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
-
- 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
-
- 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
-
- 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
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
- C30B7/105—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes using ammonia as solvent, i.e. ammonothermal processes
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of a tetrapod-like whisker reinforced silver zinc oxide contact material, which comprises the following steps: firstly, sequentially adding ammonia water and hexadecyl trimethyl ammonium bromide into a zinc nitrate solution, heating and drying to obtain tetrapod-like zinc oxide whiskers; adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution, mixing, and then sequentially adding silver nitrate and PVP-K30/ethanol solution to obtain tetrapod-like zinc oxide whiskers with silver plated surfaces; then putting the tetrapod-like zinc oxide whiskers with the silver plated on the surface and silver powder into a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; and finally, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder to obtain the tetrapod-like whisker reinforced silver zinc oxide contact material. Can improve the comprehensive performance and the service life of the contact material.
Description
Technical Field
The invention belongs to the technical field of contact materials, and relates to a preparation method of a tetrapod-like whisker reinforced silver zinc oxide contact material.
Background
In switching devices, the electrical contact material plays an important role, such as the role of switching on and off circuit elements. The performance of the electrical contacts can directly affect the service life, the feasibility of use and the on-off capacity of the electrical appliance. The silver zinc oxide electrical contact material is widely used in the field of low-voltage electrical appliances due to the characteristics of the material, such as high current (3000 + 5000A) impact resistance, good breaking performance, arc erosion resistance, no toxicity and the like.
The silver zinc oxide electrical contact material is used as a metal matrix composite material, and the size, the morphology and the combination state of a reinforcing phase and a matrix have great influence on the performance of the composite material. The problems of the prior silver zinc oxide electrical contact material mainly comprise the following two points: (1) the wettability between the matrix and the reinforcing phase is poor; (2) the reinforcing phase is difficult to be uniformly dispersed in the matrix. Because the wettability between the two phases is poor and the two phases are difficult to be uniformly dispersed, the bonding state of the reinforcing phase and the matrix is poor, and under the action of long-term electric arc force and electric arc stirring, the reinforcing phase can be re-enriched and segregated and float on the surface of a silver molten pool, 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 a tetrapod-like whisker reinforced silver zinc oxide contact material, which solves the problem of uneven distribution of a reinforcing phase in a matrix in the prior art.
The invention adopts the technical scheme that a preparation method of a tetrapod-like whisker reinforced silver zinc oxide contact material comprises the following steps:
firstly, sequentially adding ammonia water and hexadecyl trimethyl ammonium bromide into a zinc nitrate solution, and obtaining tetrapod-like zinc oxide whiskers after hydrothermal treatment, washing and drying; adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution, mixing, and then sequentially adding silver nitrate and PVP-K30/ethanol solution to obtain tetrapod-like zinc oxide whiskers with silver plated surfaces; then putting the tetrapod-like zinc oxide whiskers with the silver plated on the surface and silver powder into a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; and finally, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder to obtain the tetrapod-like whisker reinforced silver zinc oxide contact material.
The invention is also characterized in that:
the method specifically comprises the following steps:
step 1, sequentially adding ammonia water and hexadecyl trimethyl ammonium bromide into a zinc nitrate solution to obtain a precursor solution; transferring the precursor solution into a reaction kettle, then placing the reaction kettle in an electric heating blast drying box for heating, cooling, and then carrying out centrifugal separation, washing and drying on precipitates in the reaction kettle to obtain tetrapod-like zinc oxide whiskers;
step 2, adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution, stirring, washing to obtain zinc oxide whiskers, dispersing the zinc oxide whiskers in distilled water to obtain a suspension, and adding a silver nitrate solution into the suspension to obtain a mixed solution; adding PVP-K30/ethanol solution into the mixed solution, stirring to obtain a precipitate, washing and drying the precipitate to obtain tetrapod-like zinc oxide whiskers with silver plated on the surface;
step 3, putting the tetrapod-like zinc oxide whiskers with the silver plated on the surface and the silver powder into a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder;
and 4, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder to obtain the tetrapod-like whisker reinforced silver zinc oxide contact material.
The concentration of the zinc nitrate solution is 0.1-0.2 mol/L, and the preparation method of the zinc nitrate solution comprises the following steps: and dissolving the hydrated zinc nitrate in deionized water, and stirring to obtain a zinc nitrate solution.
The concentration of the ammonia water is 0.5-0.6 mol/L, and the concentration of the hexadecyl trimethyl ammonium bromide is 0.05-0.1 mol/L.
The heating temperature of the electrothermal blowing drying box is 180-200 ℃, and the heat preservation time is 20-24 h.
The concentration of the stannous chloride solution is 0.05-0.1mol/L, and the preparation method of the stannous chloride solution comprises the following steps: and (3) fully dissolving stannous chloride in deionized water to obtain a stannous chloride solution.
And 2, the content of the zinc oxide whiskers in the suspension liquid is 8-12 g/L, the concentration of the silver nitrate solution is 0.07-0.1 mol/L, and the content of PVP-K30 in the PVP-K30/ethanol solution is 60-80 g/L.
The mixing ratio of the tetrapod-like zinc oxide whiskers to the silver powder in the step 3 is 88-92: 8-12.
The ball milling process parameters are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the number ratio of the grinding balls is 1:1:2, the ball material ratio is 8-10: 1, the ball milling rotating speed is 400-600 r/min, and the ball milling time is 4-6 h.
And 4, sintering the discharge plasma sintering at the sintering temperature of 800-850 ℃ for 1-1.5 h, at the heating rate of 80-100 ℃/min and under the loading pressure of 30-50 Mpa.
The invention has the beneficial effects that:
according to the preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material, a reinforcing phase is changed from traditional zinc oxide particles into tetrapod-like zinc oxide whiskers with a unique spatial structure and excellent performance, and the prepared silver zinc oxide electrical contact material has the characteristic of isotropy; the bonding state between the matrix and the reinforcing phase is improved by coating silver on the surface of the reinforcing phase in the electrical contact material, so that the reinforcing phase is tightly bonded with the matrix, the defects and cavities in the material are reduced, and the comprehensive performance of the material is improved; due to the unique spatial structure (skeleton constraint effect) of the enhanced phase and the silver coating treatment on the surface of the enhanced phase, the situation that the enhanced phase is separated from a silver matrix and enriched on the surface of a contact under the action of long-term electric arc can be effectively avoided, the uniformity of a second phase is further maintained, and the service life of the material is prolonged; the SPS plasma sintering is used for replacing the traditional extrusion-sintering-repressing-reheating preparation process, so that the production steps are greatly simplified, the working efficiency is improved, and meanwhile, the material obtained by the plasma sintering has higher density, better comprehensive performance and fewer defect gaps.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
A preparation method of a tetrapod-like whisker reinforced silver zinc oxide contact material specifically comprises the following steps:
step 1, sequentially adding ammonia water and hexadecyl trimethyl ammonium bromide into a zinc nitrate solution, and carrying out hydrothermal treatment, washing and drying to obtain tetrapod-like zinc oxide whiskers;
step 1.1, dissolving hydrated zinc nitrate in deionized water, and stirring to obtain a zinc nitrate solution with the concentration of 0.1-0.2 mol/L;
step 1.2, sequentially adding 0.5-0.6 mol/L ammonia water and 0.05-0.1mol/L hexadecyl trimethyl ammonium bromide into a zinc nitrate solution to obtain a precursor solution;
step 1.3, transferring the precursor solution into a reaction kettle, then placing the reaction kettle in an electric heating air blowing drying box, heating to 180-200 ℃, and keeping the temperature for 20-24 hours;
and step 1.4, taking out the white precipitate in the reaction kettle, naturally cooling to room temperature, then carrying out centrifugal separation, sequentially washing with absolute ethyl alcohol and deionized water for 2-3 times, and drying in a vacuum drying oven at 60-80 ℃ to constant weight to obtain the tetrapod-like zinc oxide whisker.
Step 2, adding the tetrapod-like zinc oxide whiskers into stannous chloride solution, mixing, and then sequentially adding silver nitrate and PVP-K30/ethanol solution to obtain tetrapod-like zinc oxide whiskers with silver plated on the surface;
2.1, fully dissolving stannous chloride in deionized water to obtain a stannous chloride solution with the concentration of 0.05-0.1 mol/L;
step 2.2, adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution, stirring for 20-40 min, and washing with deionized water for multiple times to obtain sensitized zinc oxide whiskers;
step 2.3, dispersing zinc oxide whiskers in distilled water to obtain a suspension with the zinc oxide whisker content of 8-12 g/L, adding 0.07-0.1 mol/L of silver nitrate solution into the suspension, and magnetically stirring for 1-1.5 hours to obtain a mixed solution;
and 2.4, dissolving PVP-K30 in absolute ethyl alcohol to obtain a PVP-K30/ethanol solution with the PVP-K30 content of 60-80 g/L, adding the PVP-K30/ethanol solution into the mixed solution, carrying out magnetic stirring for 2-2.5 hours to obtain a precipitate, washing and drying the precipitate to obtain the tetrapod-like zinc oxide whisker with silver plated on the surface.
Step 3, mixing the tetrapod-like zinc oxide whiskers with the silver plated on the surface and the silver powder according to a ratio of 88-92:8-12, and then placing the mixture in a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; the ball milling process parameters are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the number ratio of the grinding balls is 1:1:2, the ball material ratio is 8-10: 1, the ball milling rotating speed is 400-600 r/min, and the ball milling time is 4-6 h.
Step 4, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder under a vacuum condition to obtain a tetrapod-like whisker reinforced silver zinc oxide contact material; the sintering temperature of the spark plasma sintering is 800-850 ℃, the sintering time is 1-1.5 h, the heating rate is 80-100 ℃/min, and the loading pressure is 30-50 Mpa.
The tetrapod-like zinc oxide whisker is the only whisker with a regular three-dimensional space structure in all whisker species. The crystal structure is complete, the internal defects are few, and the physical properties of all aspects are very excellent. The four-needle zinc oxide is introduced into the silver zinc oxide electrical contact material, so that the formation of defects can be effectively reduced, the mechanical property of the electrical contact material is improved, and the service life of the electrical contact material is prolonged. Secondly, the unique spatial structure makes it possible to achieve a three-dimensional uniform distribution in the matrix, so that the electrical contact material made of the material as a reinforcing phase has isotropic properties, while general one-dimensional fibrous whiskers are difficult to achieve a three-dimensional uniform distribution in the matrix material, resulting in anisotropy of the composite material properties.
Through the mode, according to the preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material, the reinforcing phase is changed from the traditional zinc oxide particles into the tetrapod-like zinc oxide whiskers with a unique spatial structure and excellent performance, and the prepared silver zinc oxide electrical contact material has the isotropic characteristic; the bonding state between the matrix and the reinforcing phase is improved by coating silver on the surface of the reinforcing phase in the electrical contact material, so that the reinforcing phase is tightly bonded with the matrix, the defects and cavities in the material are reduced, and the comprehensive performance of the material is improved; due to the unique spatial structure (skeleton constraint effect) of the enhanced phase and the silver coating treatment on the surface of the enhanced phase, the situation that the enhanced phase is separated from a silver matrix and enriched on the surface of a contact under the action of long-term electric arc can be effectively avoided, the uniformity of a second phase is further maintained, and the service life of the material is prolonged; the SPS plasma sintering is used for replacing the traditional extrusion-sintering-repressing-reheating preparation process, so that the production steps are greatly simplified, the working efficiency is improved, and meanwhile, the material obtained by the plasma sintering has higher density, better comprehensive performance and fewer defect gaps.
Example 1
Step 1, sequentially adding 0.55mol/L ammonia water and 0.075mol/L hexadecyl trimethyl ammonium bromide into a zinc nitrate solution with the concentration of 0.15mol/L to obtain a precursor solution; transferring the precursor solution into a reaction kettle, then placing the reaction kettle in an electric heating blowing drying oven to heat to 190 ℃, and keeping the temperature for 22 hours; taking out the white precipitate in the reaction kettle, naturally cooling to room temperature, performing centrifugal separation, sequentially washing with absolute ethyl alcohol and deionized water for 2-3 times, and drying in a vacuum drying oven at 70 ℃ to constant weight to obtain tetrapod-like zinc oxide whiskers;
step 2, adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution with the concentration of 0.075mol/L, stirring for 30min, and washing for multiple times by using deionized water to obtain sensitized zinc oxide whiskers; dispersing zinc oxide whiskers in distilled water to obtain suspension with the zinc oxide whisker content of 10g/L, adding 0.08mol/L silver nitrate solution into the suspension, and magnetically stirring for 1.25h to obtain mixed solution; dissolving PVP-K30 in absolute ethyl alcohol to obtain a PVP-K30/ethanol solution with the PVP-K30 content of 70g/L, adding the PVP-K30/ethanol solution into the mixed solution, carrying out magnetic stirring for 2.25 hours to obtain a precipitate, washing and drying the precipitate to obtain tetrapod-shaped zinc oxide whiskers with silver plated surfaces;
step 3, mixing the tetrapod-like zinc oxide whiskers with the silver plated on the surface and the silver powder according to a ratio of 90:10, and then placing the mixture in a ball mill for full mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; the ball milling process parameters are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the number ratio of the grinding balls is 1:1:2, the ball-material ratio is 9:1, the ball-milling rotating speed is 500r/min, and the ball-milling time is 5 hours;
step 4, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder under a vacuum condition to obtain a tetrapod-like whisker reinforced silver zinc oxide contact material; the sintering temperature of the spark plasma sintering is 820 ℃, the sintering time is 1.25h, the heating rate is 90 ℃/min, and the loading pressure is 40 Mpa.
Example 2
Step 1, sequentially adding 0.5mol/L ammonia water and 0.05mol/L hexadecyl trimethyl ammonium bromide into a zinc nitrate solution with the concentration of 0.1mol/L to obtain a precursor solution; transferring the precursor solution into a reaction kettle, and then placing the reaction kettle in an electric heating air blowing drying box to heat to 180 ℃, and keeping the temperature for 20 hours; taking out the white precipitate in the reaction kettle, naturally cooling to room temperature, performing centrifugal separation, sequentially washing with absolute ethyl alcohol and deionized water for 2-3 times, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain tetrapod-like zinc oxide whiskers;
step 2, adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution with the concentration of 0.05mol/L, stirring for 20min, and washing with deionized water for multiple times to obtain sensitized zinc oxide whiskers; dispersing zinc oxide whiskers in distilled water to obtain suspension with the zinc oxide whisker content of 8g/L, adding 0.07mol/L silver nitrate solution into the suspension, and magnetically stirring for 1h to obtain mixed solution; dissolving PVP-K30 in absolute ethyl alcohol to obtain a PVP-K30/ethanol solution with the PVP-K30 content of 60g/L, adding the PVP-K30/ethanol solution into the mixed solution, carrying out magnetic stirring for 2 hours to obtain a precipitate, washing and drying the precipitate to obtain tetrapod-shaped zinc oxide whiskers with silver plated surfaces;
step 3, mixing the tetrapod-like zinc oxide whiskers with the silver plated on the surface and the silver powder according to a ratio of 88:12, and then placing the mixture in a ball mill for full mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; the ball milling process parameters are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the number ratio of the grinding balls is 1:1:2, the ball-material ratio is 8:1, the ball-milling rotating speed is 400r/min, and the ball-milling time is 4 hours;
step 4, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder under a vacuum condition to obtain a tetrapod-like whisker reinforced silver zinc oxide contact material; the sintering temperature of the spark plasma sintering is 800 ℃, the sintering time is 1h, the heating rate is 80 ℃/min, and the loading pressure is 30 Mpa.
Example 3
Step 1, sequentially adding 0.6mol/L ammonia water and 0.1mol/L hexadecyl trimethyl ammonium bromide into a zinc nitrate solution with the concentration of 0.2mol/L to obtain a precursor solution; transferring the precursor solution into a reaction kettle, and then placing the reaction kettle in an electric heating blowing drying oven to heat to 200 ℃, and keeping the temperature for 24 hours; taking out the white precipitate in the reaction kettle, naturally cooling to room temperature, performing centrifugal separation, sequentially washing with absolute ethyl alcohol and deionized water for 2-3 times, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain tetrapod-like zinc oxide whiskers;
step 2, adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution with the concentration of 0.1mol/L, stirring for 40min, and washing with deionized water for multiple times to obtain sensitized zinc oxide whiskers; dispersing zinc oxide whiskers in distilled water to obtain suspension with the zinc oxide whisker content of 12g/L, adding 0.1mol/L silver nitrate solution into the suspension, and magnetically stirring for 1.5h to obtain mixed solution; dissolving PVP-K30 in absolute ethyl alcohol to obtain a PVP-K30/ethanol solution with the PVP-K30 content of 80g/L, adding the PVP-K30/ethanol solution into the mixed solution, carrying out magnetic stirring for 2.5 hours to obtain a precipitate, washing and drying the precipitate to obtain tetrapod-shaped zinc oxide whiskers with silver plated surfaces;
step 3, mixing the tetrapod-like zinc oxide whiskers with the silver plated on the surface and the silver powder according to a ratio of 92:8, and then placing the mixture in a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; the ball milling process parameters are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the number ratio of the grinding balls is 1:1:2, the ball-material ratio is 10:1, the ball-milling rotating speed is 600r/min, and the ball-milling time is 6 hours;
step 4, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder under a vacuum condition to obtain a tetrapod-like whisker reinforced silver zinc oxide contact material; the sintering temperature of the spark plasma sintering is 850 ℃, the sintering time is 1.5h, the heating rate is 100 ℃/min, and the loading pressure is 50 Mpa.
Claims (10)
1. A preparation method of a tetrapod-like whisker reinforced silver zinc oxide contact material is characterized by comprising the following steps:
firstly, sequentially adding ammonia water and hexadecyl trimethyl ammonium bromide into a zinc nitrate solution, and obtaining tetrapod-like zinc oxide whiskers after hydrothermal treatment, washing and drying; adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution, mixing, and then sequentially adding silver nitrate and a PVP-K30/ethanol solution to obtain tetrapod-like zinc oxide whiskers with silvered surfaces; then, putting the tetrapod-like zinc oxide whiskers with the silver plated on the surface and silver powder into a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder; and finally, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder to obtain the tetrapod-like whisker reinforced silver zinc oxide contact material.
2. The preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material according to claim 1, which is characterized by comprising the following steps of:
step 1, sequentially adding ammonia water and hexadecyl trimethyl ammonium bromide into a zinc nitrate solution to obtain a precursor solution; transferring the precursor solution into a reaction kettle, then placing the reaction kettle in an electric heating blast drying oven for heating, cooling, and then carrying out centrifugal separation, washing and drying on precipitates in the reaction kettle to obtain tetrapod-like zinc oxide whiskers;
step 2, adding the tetrapod-like zinc oxide whiskers into a stannous chloride solution, stirring, washing to obtain zinc oxide whiskers, dispersing the zinc oxide whiskers in distilled water to obtain a suspension, and adding a silver nitrate solution into the suspension to obtain a mixed solution; adding PVP-K30/ethanol solution into the mixed solution, stirring to obtain a precipitate, washing and drying the precipitate to obtain tetrapod-like zinc oxide whiskers with silver plated on the surface;
step 3, putting the tetrapod-like zinc oxide whiskers with the silver plated on the surface and silver powder into a ball mill for fully mixing to obtain tetrapod-like whisker reinforced silver zinc oxide composite powder;
and 4, performing discharge plasma sintering on the tetrapod-like whisker reinforced silver zinc oxide composite powder to obtain the tetrapod-like whisker reinforced silver zinc oxide contact material.
3. The preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material as claimed in claim 1, wherein the concentration of the zinc nitrate solution is 0.1-0.2 mol/L, and the preparation method of the zinc nitrate solution comprises the following steps: and dissolving the hydrated zinc nitrate in deionized water, and stirring to obtain a zinc nitrate solution.
4. The method for preparing the tetrapod-like whisker reinforced silver zinc oxide contact material according to claim 1, wherein the concentration of the ammonia water is 0.5-0.6 mol/L, and the concentration of the hexadecyl trimethyl ammonium bromide is 0.05-0.1 mol/L.
5. The preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material as claimed in claim 1, wherein the heating temperature of the electrothermal blowing drying oven is 180-200 ℃, and the heat preservation time is 20-24 h.
6. The preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material according to claim 1, wherein the concentration of the stannous chloride solution is 0.05-0.1mol/L, and the preparation method of the stannous chloride solution comprises the following steps: and (3) fully dissolving stannous chloride in deionized water to obtain a stannous chloride solution.
7. The method for preparing the tetrapod-like whisker reinforced silver zinc oxide contact material according to claim 1, wherein the content of zinc oxide whiskers in the suspension in the step 2 is 8-12 g/L, the concentration of the silver nitrate solution is 0.07-0.1 mol/L, and the content of PVP-K30 in the PVP-K30/ethanol solution is 60-80 g/L.
8. The method for preparing the tetrapod-like whisker reinforced silver zinc oxide contact material according to claim 1, wherein the mixing ratio of the tetrapod-like zinc oxide whiskers to the silver powder in the step 3 is 88-92: 8-12.
9. The preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material according to claim 1, wherein the ball milling process parameters are as follows: the grinding balls are alumina grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the number ratio of the grinding balls is 1:1:2, the ball material ratio is 8-10: 1, the ball grinding rotating speed is 400-600 r/min, and the ball grinding time is 4-6 h.
10. The preparation method of the tetrapod-like whisker reinforced silver zinc oxide contact material as claimed in claim 1, wherein the sintering temperature of the spark plasma sintering in the step 4 is 800-850 ℃, the sintering time is 1-1.5 h, the heating rate is 80-100 ℃/min, and the loading pressure is 30-50 Mpa.
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