CN112239350B - Preparation method of copper tin oxide contact material - Google Patents
Preparation method of copper tin oxide contact material Download PDFInfo
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- CN112239350B CN112239350B CN202011119651.4A CN202011119651A CN112239350B CN 112239350 B CN112239350 B CN 112239350B CN 202011119651 A CN202011119651 A CN 202011119651A CN 112239350 B CN112239350 B CN 112239350B
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- HOFIJBMBYYEBNM-UHFFFAOYSA-N copper;oxotin Chemical compound [Cu].[Sn]=O HOFIJBMBYYEBNM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 54
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 238000003825 pressing Methods 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 239000002202 Polyethylene glycol Substances 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 abstract description 14
- 230000003628 erosive effect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 230000003014 reinforcing effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- KKHJTSPUUIRIOP-UHFFFAOYSA-J tetrachlorostannane;hydrate Chemical compound O.Cl[Sn](Cl)(Cl)Cl KKHJTSPUUIRIOP-UHFFFAOYSA-J 0.000 description 2
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
Abstract
The invention discloses a preparation method of a copper tin oxide contact material, which is implemented according to the following steps: step 1, preparing tin oxide microspheres; step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder; step 3, pressing and sintering the copper-tin oxide composite powder to obtain a copper-tin oxide contact material; the problem of poor wettability between a matrix and the reinforced phase in the existing copper tin oxide contact material can be solved, the arc erosion resistance of the copper tin oxide contact material is improved, and the service life of the copper tin oxide contact material is prolonged.
Description
Technical Field
The invention belongs to the technical field of material preparation processes, and particularly relates to a preparation method of a copper tin oxide contact material.
Background
The contact material is a core component of an electrical appliance switch, bears the tasks of connecting and disconnecting a circuit and loading current, and is widely used in various electrical appliance contact systems. At present, the contact material for the low-voltage electrical appliance is mainly a silver-based contact material, and the silver-based contact material consumes a large amount of noble metal silver which is scarce in resources and expensive in price. In addition, the Ag-CdO contact material with the best comprehensive performance is easy to generate toxic gas with higher toxicity in the use process, and the application range of the Ag-CdO contact material is limited to a great extent.
Copper is a common structural and functional metal material, has excellent thermal conductivity and electrical conductivity and is widely applied to various fields, and meanwhile, the copper serving as a contact material has the advantages of large heat capacity, low contact temperature rise, high hardness, short arcing time and the like. Currently, copper-based contacts are primarily composed of two components: (1) metal copper or copper-based alloy with good conductivity; (2) an enhanced phase with staged arcing capabilities. Copper tin oxide is the copper-based contact material, however, because the wettability between a copper matrix and the reinforcing phase tin oxide in the contact material is poor, the combination of the matrix and the reinforcement is not tight, cracks are easy to generate and quickly expand under the action of heat-force cyclic load, and the comprehensive performance and the service life of the material are greatly reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a copper tin oxide contact material, which can solve the problem of poor wettability between a matrix and an enhanced phase in the existing copper tin oxide contact material, improve the arc erosion resistance of the copper tin oxide contact material and prolong the service life of the copper tin oxide contact material.
The technical scheme adopted by the invention is that the preparation method of the copper tin oxide contact material is implemented according to the following steps:
step 1, preparing tin oxide microspheres;
step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder;
and 3, pressing and sintering the copper-tin oxide composite powder to obtain the copper-tin oxide contact material.
The invention is also characterized in that:
the specific process of the step 1 is as follows:
step 1.1, fully dissolving tin tetrachloride pentahydrate and urea in a mixed solution of absolute ethyl alcohol and DMF, and fully stirring to obtain a solution a;
step 1.2, dissolving polyethylene glycol in a mixed solution of absolute ethyl alcohol and deionized water, and fully stirring to obtain a solution b;
step 1.3, dropwise adding the solution b into the solution a, wherein the volume ratio of the solution b to the solution a is 1: 0.4-0.6, performing magnetic stirring for 20-30 min, then quickly transferring the mixed solution into a sealed reaction kettle, and putting the reaction kettle into an electrothermal blowing dry box for reaction;
and step 1.4, taking out the reaction kettle, naturally cooling to room temperature, washing the precipitate for 2-3 times by using absolute ethyl alcohol and deionized water, and placing the washed precipitate in a vacuum drying oven to dry the washed precipitate to constant weight to obtain the tin oxide microspheres with smooth surfaces, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles.
In the step 1.1, the concentration of the stannic chloride solution in the solution a is 0.02-0.05 mol/L, and the concentration of the urea is 0.005-0.01 mol/L.
In the step 1.1, the volume ratio of the absolute ethyl alcohol to the DMF is 1: 0.8-1.2.
In the step 1.2, the molecular weight of polyethylene glycol is not less than 6000, the concentration of polyethylene glycol in the solution b is 0.0005-0.0006mol/L, and the volume ratio of absolute ethyl alcohol to deionized water is 1: 0.8-1.0.
In the step 1.3, the reaction temperature of the reaction in the electrothermal blowing drying oven is 180-200 ℃, and the reaction time is 10-12 h.
And step 1.4, placing the mixture in a vacuum drying oven to be dried until the drying temperature of the constant weight is 60-70 ℃, and the drying time is 20-30 min.
Step 2, the ball milling technological parameters are as follows: the mass ratio of the copper powder to the lanthanum powder to the tin oxide microspheres is 95.56-96.22: 0.24-0.18: 4.2-3.6, putting the ball material in a horizontal planetary ball mill, wherein the grinding balls are zirconia grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, and the ball material mass ratio is as follows according to the quantity ratio of 1:1: 2: 6-10: 1, the ball milling speed is 300-400 r/min, and the ball milling time is 3-4 h.
The specific process of the step 3 is as follows:
step 3.1, placing the copper-tin oxide composite powder in a cold pressing die for primary pressing, taking out the copper-tin oxide composite powder, placing the copper-tin oxide composite powder in a tubular furnace for sintering, wherein the sintering temperature is 900-950 ℃, and keeping the temperature for 2-3 hours;
and 3.2, taking out the copper-tin oxide contact material, putting the copper-tin oxide contact material into a cold pressing mold for re-pressing, performing re-sintering at the sintering temperature of 850-900 ℃ for 2-2.5 hours, and cooling to obtain the copper-tin oxide contact material.
The sintering process of step 3.1 and step 3.2 is carried out under vacuum condition or inert atmosphere.
The invention has the beneficial effects that:
the invention relates to a preparation method of a copper tin oxide contact material, which is characterized in that tin chloride hydrate is used as a tin source by a solvothermal method, polyethylene glycol is used as a surfactant to prepare tin oxide microspheres with smooth surfaces, the tin oxide microspheres are assembled by tin oxide nanoparticles, the diameter of each microsphere is about 0.6-0.8 mu m, the size of each nanocrystal is about 5-10 nm, a certain amount of metal lanthanum powder is introduced to improve the wettability of a matrix and an enhanced phase, then high-energy ball milling is used for mixing powder to obtain copper/lanthanum/tin oxide composite powder, and the copper tin oxide contact material is obtained after initial pressing, sintering, re-pressing and re-sintering.
The second-phase oxide in the copper tin oxide contact material is the tin oxide solid microspheres which have good dispersibility and are self-assembled by the nanocrystalline, the oxide is uniformly distributed, the dispersibility of the second-phase tin oxide in a copper matrix is improved, the tin oxide solid microspheres are selected as a reinforcing phase, the situation that the reinforcing phase is separated from the matrix and enriched on the surface of the contact under the action of arc erosion can be avoided, meanwhile, metal lanthanum is introduced in the preparation process to improve the wettability between the matrix and the reinforcing phase, the bonding state between the matrix and the reinforcing body is improved, and the copper tin oxide contact material with excellent comprehensive performance and long service life is obtained.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of a copper tin oxide contact material, which is implemented according to the following steps:
step 1, preparing tin oxide microspheres;
the specific process of the step 1 is as follows:
step 1.1, fully dissolving tin tetrachloride pentahydrate and urea in a mixed solution of absolute ethyl alcohol and DMF, and fully stirring to obtain a solution a;
the volume ratio of the absolute ethyl alcohol to the DMF is 1: 0.8-1.2.
The concentration of the stannic chloride solution in the solution a is 0.02-0.05 mol/L, and the concentration of the urea is 0.005-0.01 mol/L.
Step 1.2, dissolving polyethylene glycol in a mixed solution of absolute ethyl alcohol and deionized water, and fully stirring to obtain a solution b;
the molecular weight of the polyethylene glycol is not less than 6000, the finally obtained product is microspheres with good dispersibility formed by assembling nano particles, if the molecular weight of the polyethylene glycol is too small, most of the molding differences of the microspheres are irregular spheres or even the microspheres cannot be molded, the size of the microspheres is increased and the sphericity is better and better along with the increase of the molecular weight, the concentration of the polyethylene glycol in the solution b is 0.0005-0.0006mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 0.8-1.0.
Step 1.3, dropwise adding the solution b into the solution a, wherein the volume ratio of the solution b to the solution a is 1: 0.4-0.6, performing magnetic stirring for 20-30 min, then quickly transferring the mixed solution into a sealed reaction kettle, and putting the reaction kettle into an electrothermal blowing dry box for reaction;
the reaction temperature of the mixture put into an electrothermal blowing dry box for reaction is 180-200 ℃, and the reaction time is 10-12 h.
And step 1.4, taking out the reaction kettle, naturally cooling to room temperature, washing the precipitate for 2-3 times by using absolute ethyl alcohol and deionized water, and placing the washed precipitate in a vacuum drying oven to dry the washed precipitate to constant weight to obtain the tin oxide microspheres with smooth surfaces, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles.
And (3) placing the mixture in a vacuum drying oven to be dried until the drying temperature of the constant weight is 60-70 ℃, and the drying time is 20-30 min.
The diameter of the obtained tin oxide microsphere is about 0.6-0.8 mu m, and Sn is obtained under the solvothermal condition 4+ With OH - Carrying out interaction, dehydration and decomposition to generate nano particles; the surfaces of the nano particles are coated with PEG6000 macromolecular chains and are aggregated to form orientation arrangement; the microspheres are further assembled to form microspheres in order to reduce free energy.
Step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder;
the ball milling process parameters are as follows: the grinding balls are zirconia grinding balls with the diameters of 10mm, 8mm and 6mm respectively, and are mixed according to the quantity ratio of 1:1:2, and the ball material mass ratio is as follows: 1: 6-10, the ball milling speed is 300-400 r/min, the ball milling time is 3-4 h, and the mass ratio of the copper powder, the lanthanum powder and the tin oxide microspheres is 95.56-96.22: 0.24-0.18: 4.2 to 3.6.
And 3, pressing and sintering the copper-tin oxide composite powder to obtain the copper-tin oxide contact material.
The specific process of the step 3 is as follows:
step 3.1, placing the copper-tin oxide composite powder in a cold pressing die for primary pressing, taking out the copper-tin oxide composite powder, placing the copper-tin oxide composite powder in a tubular furnace for sintering, wherein the sintering temperature is 900-950 ℃, and keeping the temperature for 2-3 hours;
and 3.2, taking out the copper-tin oxide contact material, putting the copper-tin oxide contact material into a cold pressing mold for re-pressing, performing re-sintering at the sintering temperature of 850-900 ℃ for 2-2.5 hours, and cooling to obtain the copper-tin oxide contact material.
The sintering process of step 3.1 and step 3.2 is carried out under vacuum condition or inert atmosphere.
Example 1
A preparation method of a copper tin oxide contact material is implemented according to the following steps:
step 1, preparing tin oxide microspheres;
the specific process of the step 1 is as follows:
step 1.1, fully dissolving tin tetrachloride pentahydrate and urea in a mixed solution of absolute ethyl alcohol and DMF, and fully stirring to obtain a solution a;
the volume ratio of the absolute ethyl alcohol to the DMF is 1: 0.8.
The concentration of the stannic chloride solution in the solution a is 0.02mol/L, and the concentration of the urea is 0.005 mol/L.
Step 1.2, dissolving polyethylene glycol in a mixed solution of absolute ethyl alcohol and deionized water, and fully stirring to obtain a solution b;
the molecular weight of the polyethylene glycol is 6000, the concentration of the polyethylene glycol in the solution b is 0.0005mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 0.8.
Step 1.3, dropwise adding the solution b into the solution a, wherein the volume ratio of the solution b to the solution a is 1: 0.4, carrying out magnetic stirring for 20min, then quickly transferring the mixed solution into a sealed reaction kettle, and putting the reaction kettle into an electrothermal blowing dry box for reaction;
the reaction temperature of the mixture put into an electric heating forced air drying oven for reaction is 180 ℃, and the reaction time is 10 hours.
And step 1.4, taking out the reaction kettle, naturally cooling to room temperature, washing the precipitate for 2 times by using absolute ethyl alcohol and deionized water, and placing the washed precipitate in a vacuum drying oven to dry to constant weight to obtain the tin oxide microspheres with smooth surfaces, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles.
Drying in a vacuum drying oven at constant weight at 60 deg.C for 20 min.
Step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder;
the ball milling process parameters are as follows: the grinding balls are zirconia grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, the ball-milling speed is 300r/min, the ball-milling time is 3h, the mass ratio of copper powder, lanthanum powder and tin oxide microspheres is 95.56: 0.24: 4.2.
and 3, pressing and sintering the copper-tin oxide composite powder to obtain the copper-tin oxide contact material.
The specific process of the step 3 is as follows:
step 3.1, carrying out primary pressing on the copper-tin oxide composite powder at the pressure of 300MPa, taking out, and then sintering at the sintering temperature of 900 ℃ for 2 h;
and 3.2, taking out the copper-tin oxide contact material, then carrying out re-pressing with the re-pressing pressure of 950MPa, then carrying out re-sintering at the sintering temperature of 850 ℃ for 2h, and cooling to obtain the copper-tin oxide contact material.
The sintering process of step 3.1 and step 3.2 is carried out under vacuum condition or inert atmosphere.
Example 2
A preparation method of a copper tin oxide contact material is implemented according to the following steps:
step 1, preparing tin oxide microspheres;
the specific process of the step 1 is as follows:
step 1.1, fully dissolving tin tetrachloride pentahydrate and urea in a mixed solution of absolute ethyl alcohol and DMF, and fully stirring to obtain a solution a;
the volume ratio of the absolute ethyl alcohol to the DMF is 1:1.
The concentration of the tin chloride solution in the solution a is 0.03mol/L, and the concentration of the urea is 0.007 mol/L.
Step 1.2, dissolving polyethylene glycol in a mixed solution of absolute ethyl alcohol and deionized water, and fully stirring to obtain a solution b;
the molecular weight of the polyethylene glycol is 6000, the concentration of the polyethylene glycol in the solution b is 0.00054mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 0.9.
Step 1.3, dropwise adding the solution b into the solution a, wherein the volume ratio of the solution b to the solution a is 1: 0.5, carrying out magnetic stirring for 25min, then quickly transferring the mixed solution into a sealed reaction kettle, and putting the reaction kettle into an electrothermal blowing dry box for reaction;
the reaction temperature of the mixture put into an electric heating forced air drying oven for reaction is 190 ℃, and the reaction time is 11 hours.
And step 1.4, taking out the reaction kettle, naturally cooling to room temperature, washing the precipitate for 2 times by using absolute ethyl alcohol and deionized water, and placing the washed precipitate in a vacuum drying oven to dry to constant weight to obtain the tin oxide microspheres with smooth surfaces, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles.
Drying in a vacuum drying oven at constant weight of 65 deg.C for 25 min.
Step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder;
the ball milling process parameters are as follows: the grinding balls are zirconia grinding balls with the diameters of 10mm, 8mm and 6mm respectively, and are mixed according to the quantity ratio of 1:1:2, and the ball material mass ratio is as follows: 8:1, ball milling speed of 350r/min, ball milling time of 3.5h, mass ratio of copper powder, lanthanum powder and tin oxide microspheres of 96: 0.2: 3.8.
and 3, pressing and sintering the copper-tin oxide composite powder to obtain the copper-tin oxide contact material.
The specific process of the step 3 is as follows:
step 3.1, carrying out primary pressing on the copper-tin oxide composite powder at the pressure of 350MPa, taking out, and then sintering, wherein the sintering temperature is 920 ℃, and keeping the temperature for 2.5 h;
and 3.2, taking out the copper-tin oxide contact material, then carrying out re-pressing with the re-pressing pressure of 980MPa, then carrying out re-sintering with the sintering temperature of 880 ℃, preserving heat for 2.3h, and cooling to obtain the copper-tin oxide contact material.
The sintering process of step 3.1 and step 3.2 is carried out under vacuum condition or inert atmosphere.
Example 3
A preparation method of a copper tin oxide contact material is implemented according to the following steps:
step 1, preparing tin oxide microspheres;
the specific process of the step 1 is as follows:
step 1.1, fully dissolving tin tetrachloride pentahydrate and urea in a mixed solution of absolute ethyl alcohol and DMF, and fully stirring to obtain a solution a;
the volume ratio of the absolute ethyl alcohol to the DMF is 1: 1.2.
The concentration of the tin chloride solution in the solution a is 0.05mol/L, and the concentration of the urea is 0.01 mol/L.
Step 1.2, dissolving polyethylene glycol in a mixed solution of absolute ethyl alcohol and deionized water, and fully stirring to obtain a solution b;
the molecular weight of the polyethylene glycol is 6000, the concentration of the polyethylene glycol in the solution b is 0.0006mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1.0.
Step 1.3, dropwise adding the solution b into the solution a, wherein the volume ratio of the solution b to the solution a is 1: 0.6, carrying out magnetic stirring for 30min, then quickly transferring the mixed solution into a sealed reaction kettle, and putting the reaction kettle into an electrothermal blowing dry box for reaction;
the reaction temperature of the mixture put into an electric heating forced air drying oven for reaction is 200 ℃, and the reaction time is 12 hours.
And step 1.4, taking out the reaction kettle, naturally cooling to room temperature, washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water, and placing the washed precipitate in a vacuum drying oven to dry to constant weight to obtain the tin oxide microspheres with smooth surfaces, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles.
Drying in a vacuum drying oven at constant weight at 70 deg.C for 30 min.
Step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder;
the ball milling process parameters are as follows: the grinding balls are zirconia grinding balls with the diameters of 10mm, 8mm and 6mm respectively, and are mixed according to the quantity ratio of 1:1:2, and the ball material mass ratio is as follows: 10:1, ball milling rotation speed of 400r/min, ball milling time of 4h, mass ratio of copper powder, lanthanum powder and tin oxide microspheres of 96.22: 0.18: 3.6.
and 3, pressing and sintering the copper-tin oxide composite powder to obtain the copper-tin oxide contact material.
The specific process of the step 3 is as follows:
step 3.1, carrying out primary pressing on the copper-tin oxide composite powder at the pressure of 400MPa, taking out, and then sintering, wherein the sintering temperature is 950 ℃, and preserving heat for 3 hours;
and 3.2, taking out the copper-tin oxide contact material, then carrying out re-pressing with the re-pressing pressure of 1000MPa, then carrying out re-sintering with the sintering temperature of 900 ℃ and keeping the temperature for 2.5h, and cooling to obtain the copper-tin oxide contact material.
The sintering process of step 3.1 and step 3.2 is carried out under vacuum condition or inert atmosphere.
The preparation method of the copper tin oxide contact material has the following beneficial effects:
the method comprises the steps of preparing tin oxide microspheres with smooth surfaces by using a solvothermal method, using tin chloride hydrate as a tin source and using polyethylene glycol as a surfactant, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles, the diameter of each microsphere is about 0.6-0.8 mu m, the size of each nanocrystal is about 5-10 nm, introducing a certain amount of metal lanthanum powder to improve the wettability of a matrix and enhance interphase, mixing the powder by using high-energy ball milling to obtain copper/lanthanum/tin oxide composite powder, and carrying out primary pressing, sintering, re-pressing and re-sintering to obtain the copper-tin oxide contact material.
The second-phase oxide in the copper tin oxide contact material is the tin oxide solid microspheres which have good dispersibility and are self-assembled by the nanocrystalline, the oxide is uniformly distributed, the dispersibility of the second-phase tin oxide in a copper matrix is improved, the tin oxide solid microspheres are selected as a reinforcing phase, the situation that the reinforcing phase is separated from the matrix and enriched on the surface of the contact under the action of arc erosion can be avoided, meanwhile, metal lanthanum is introduced in the preparation process to improve the wettability between the matrix and the reinforcing phase, the bonding state between the matrix and the reinforcing body is improved, and the copper tin oxide contact material with excellent comprehensive performance and long service life is obtained.
Claims (6)
1. The preparation method of the copper tin oxide contact material is characterized by comprising the following steps:
step 1, preparing tin oxide microspheres; the specific process is as follows:
step 1.1, fully dissolving tin tetrachloride pentahydrate and urea in a mixed solution of absolute ethyl alcohol and DMF, and fully stirring to obtain a solution a;
the concentration of the stannic chloride solution in the solution a is 0.02-0.05 mol/L, and the concentration of the urea is 0.005-0.01 mol/L;
step 1.2, dissolving polyethylene glycol in a mixed solution of absolute ethyl alcohol and deionized water, and fully stirring to obtain a solution b;
step 1.3, dropwise adding the solution b into the solution a, wherein the volume ratio of the solution b to the solution a is 1: 0.4-0.6, performing magnetic stirring for 20-30 min, then quickly transferring the mixed solution into a sealed reaction kettle, and putting the reaction kettle into an electrothermal blowing dry box for reaction;
step 1.4, taking out the reaction kettle, naturally cooling to room temperature, washing the precipitate for 2-3 times by using absolute ethyl alcohol and deionized water, and placing the washed precipitate in a vacuum drying oven to dry the washed precipitate to constant weight to obtain tin oxide microspheres with smooth surfaces, wherein the tin oxide microspheres are assembled by tin oxide nanoparticles;
step 2, placing the copper powder, the lanthanum powder and the tin oxide microspheres in a horizontal planetary ball mill for ball milling and mixing to obtain copper-tin oxide composite powder;
the ball milling process parameters are as follows: the mass ratio of the copper powder to the lanthanum powder to the tin oxide microspheres is 95.56-96.22: 0.24-0.18: 4.2-3.6, putting the ball material in a horizontal planetary ball mill, wherein the grinding balls are zirconia grinding balls, the diameters of the grinding balls are respectively 10mm, 8mm and 6mm, and the ball material mass ratio is as follows according to the quantity ratio of 1:1: 2: 1: 6-10, the ball milling speed is 300-400 r/min, and the ball milling time is 3-4 h;
step 3, pressing and sintering the copper-tin oxide composite powder to obtain a copper-tin oxide contact material;
the specific process is as follows:
step 3.1, placing the copper-tin oxide composite powder in a cold pressing die for primary pressing, taking out the copper-tin oxide composite powder, placing the copper-tin oxide composite powder in a tubular furnace for sintering, wherein the sintering temperature is 900-950 ℃, and keeping the temperature for 2-3 hours;
and 3.2, taking out the copper-tin oxide contact material, putting the copper-tin oxide contact material into a cold pressing mold for re-pressing, performing re-sintering at the sintering temperature of 850-900 ℃ for 2-2.5 hours, and cooling to obtain the copper-tin oxide contact material.
2. The method for preparing the copper tin oxide contact material according to claim 1, wherein the volume ratio of the absolute ethyl alcohol to the DMF in the step 1.1 is 1: 0.8-1.2.
3. The method for preparing the copper tin oxide contact material according to claim 1, wherein the molecular weight of the polyethylene glycol in the step 1.2 is not less than 6000, the concentration of the polyethylene glycol in the solution b is 0.0005 to 0.0006mol/L, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1:0.8 to 1.0.
4. The method for preparing the copper tin oxide contact material according to claim 1, wherein the reaction temperature of the step 1.3 in the electrothermal blowing dry box is 180-200 ℃ and the reaction time is 10-12 h.
5. The method for preparing the copper tin oxide contact material according to claim 1, wherein the step 1.4 is carried out in a vacuum drying oven for drying until the drying temperature for constant weight is 60-70 ℃ and the drying time is 20-30 min.
6. The method of claim 1, wherein the step 3.1 and the step 3.2 sintering processes are performed under vacuum or inert atmosphere.
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