CN114360948A - Silver tin oxide indium oxide electric contact composite material and preparation method thereof - Google Patents
Silver tin oxide indium oxide electric contact composite material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 52
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 17
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- 238000000227 grinding Methods 0.000 claims description 32
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 14
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 230000008569 process Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical group O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- IVQODXYTQYNJFI-UHFFFAOYSA-N oxotin;silver Chemical compound [Ag].[Sn]=O IVQODXYTQYNJFI-UHFFFAOYSA-N 0.000 description 2
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- 238000010008 shearing Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a silver tin oxide indium oxide electric contact composite material and a preparation method thereof, wherein the method comprises the following steps: preparing AgSnIn alloy atomized powder; the AgSnIn alloy atomized powder is used as a raw material, rare earth oxide is used as a modifier, and machinery is adoptedPreparing rare earth oxide modified AgSnIn composite powder by a chemical reaction method; placing the rare earth oxide modified AgSnIn composite powder in hot isostatic pressing equipment for reaction to obtain a rare earth oxide modified AgSnIn ingot blank; hot-extruding the rare earth oxide modified AgSnIn ingot blank into an AgSnIn-rare earth oxide plate, and carrying out post-treatment to obtain the rare earth oxide modified AgSnO2In2O3An electrical contact material. The modified AgSnO of the invention2In2O3The electric contact material constructs a special structure with solid solution particles distributed at the front end of the hierarchical dendritic crystal structure in the reaction process, and the special structure is used as a structural channel, so that the transfer of electric arc heat energy can be realized, the temperature rise of the electric contact material can be effectively improved, and the electric circulation capacity of the material can be improved.
Description
Technical Field
The invention relates to the technical field of rare earth oxide modified silver-based composite materials, in particular to rare earth oxide modified AgSnO2In2O3An electrical contact composite material and a preparation method thereof.
Background
In high-end application scenes such as 5G communication, high-voltage direct-current electrical appliances and the like, relays serving in severe environments (such as high humidity, dust, corrosive gas, explosive gas and the like) generally need to be completely sealed, but under a sealed structure, the metal oxide enhanced Ag-based electric contact composite material serving as a key material of a relay contact element is prone to have the disadvantages of high temperature rise and rapid reduction of the electric service life cycle life in the service process. In particular, when the load current of the contact element becomes large, the cycle life thereof is more seriously decreased, failing to meet the application requirements of the relay.
Based on the existing theory related to electrical contact, it is known that the temperature rise, the arc energy and the characteristics of the contact material are generally important factors affecting the electrical life of the relay, wherein the characteristics of the contact material play an especially important role in the three. For this reason, related researchers have conducted research on the improvement of the optimization of the characteristics of a series of materials.
For example, Li-Yanlin research finds that compared with pure AgSnO2In2O3In other words, TeO is introduced2The additive can effectively improve the fusion welding resistance and reduce the arcing resistance of the AgSnO2In2O3, but the quality loss is obviously increased [ Li Yan et al, and the influence of different additives on the electrical property of AgSnO2In2O3 contact material [ J]Electrical material, 2021, 01]。
Compared with an alloy internal oxidation method, Guo jade and the like find that the doped modified AgSnO containing Ni, Cu, Bi, Te and other multiple elements and prepared by a powder pre-oxidation method2In2O3Preparation and performance research of AgSnO2In2O3 electric contact material with optimal hardness, tensile strength, arc erosion resistance and material transfer resistance by powder pre-oxidation method [ Guo jade and the like ] [ J]Electrical material 2015(5)]。
Research on Wangsong and the like finds that compared with a powder metallurgy method and an alloy powder pre-oxidation method, the AgSnO2In2O3 material with the best tissue uniformity and the best arc erosion resistance performance can be prepared by a pressurizing internal oxidation method [ Wangsong and the like, the annealing temperature has influence on the tissue and performance of an AgSnO2Y2O3 electrical contact material [ J ]. Nicoti university report (Nature science and engineering edition). 2014,27(03) ].
Through retrieval, the Chinese patent with the publication number of CN105702503B discloses a preparation method of a silver tin oxide indium oxide contact material, which comprises the following steps: (1) preparing materials; (2) carrying out water atomization on tin, indium and germanium to prepare tin-indium alloy powder; (3) oxidizing the tin-indium alloy powder into tin oxide-indium oxide composite powder under certain oxygen pressure and temperature, and granulating the oxidized powder; (4) mechanically mixing the prepared composite powder with 200-mesh 300-mesh silver powder, and uniformly mixing; (5) and (3) carrying out isostatic pressing, sintering and extruding on the mixed silver tin oxide and indium oxide composite powder, and drawing to obtain the wire with the required finished product specification. However, the invention can only improve the fusion welding resistance, the conductivity, the processability and the like of the silver tin oxide indium oxide contact material, and the service life of the contact material needs to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims atProviding a rare earth oxide modified AgSnO2In2O3An electrical contact composite material and a preparation method thereof.
According to one aspect of the invention, the rare earth oxide modified AgSnO is provided2In2O3A method of making an electrical contact composite comprising:
preparing AgSnIn alloy atomized powder;
preparing rare earth oxide modified AgSnIn composite powder by taking the AgSnIn alloy atomized powder as a raw material and rare earth oxide as a modifier by adopting a mechanochemical reaction method;
placing the rare earth oxide modified AgSnIn composite powder in hot isostatic pressing equipment for reaction to obtain a rare earth oxide modified AgSnIn ingot blank;
hot-extruding the rare earth oxide modified AgSnIn ingot blank into an AgSnIn-rare earth oxide plate, and carrying out post-treatment to obtain the rare earth oxide modified AgSnO2In2O3An electrical contact material.
Further, the preparation of the AgSnIn alloy atomized powder comprises the following steps: the method comprises the following steps of preparing AgSnIn alloy atomized powder by using Ag, Sn and In as raw materials and utilizing a supersonic speed spray granulation mode, wherein the purities of the Ag, the Sn and the In are all 99.99%.
Further, the preparation of the AgSnIn alloy atomized powder by using a supersonic speed spray granulation mode comprises the following steps: in the spraying process, the atomizing medium is nitrogen, double-side ventilation is carried out, the atomizing pressure is 0.3-0.8 MPa, and the alloy superheat degree is 100-250 ℃; and collecting powder after the powder atomization is finished, and sieving the powder by a sieve of 100-300 meshes to obtain AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
Further, the rare earth oxide is used as a modifier, and comprises the following components: the content of the rare earth oxide accounts for 1.2-4.5 wt% of the total mass of the rare earth oxide and the AgSnIn alloy atomized powder.
Further, the rare earth oxide is La2O3、Bi2O3、CeO2And Y2O3At least one of (1).
Further, the preparation of the rare earth oxide modified AgSnIn composite powder by adopting a mechanochemical reaction method comprises the following steps: the preparation method of the rare earth oxide modified AgSnIn composite powder by adopting a mechanochemical reaction method comprises the following steps: forming total powder by using rare earth oxide and AgSnIn alloy atomized powder, weighing stainless steel grinding balls according to the mass ratio of the stainless steel grinding balls to the total powder of 5-10: 1, and weighing absolute ethyl alcohol according to the mass ratio of the absolute ethyl alcohol to the total powder of 2: 1; and sequentially putting the rare earth oxide, the AgSnIn alloy atomized powder, the stainless steel grinding balls and the absolute ethyl alcohol into a ball-milling tank, and grinding for 10-25 h under the condition that the ball-milling rotating speed is 150-350 rpm.
Furthermore, the ball milling tank is made of stainless steel or agate; the stainless steel grinding ball comprises
A ball,
Ball and stomach regulating
A ball of
Ball, the
Ball, the
The weight ratio of the balls is 1:1: 1.
Further, the reaction of the rare earth oxide modified AgSnIn composite powder in a hot isostatic pressing machine device comprises the following steps: and filling the rare earth oxide modified AgSnIn composite powder into a steel sheath, degassing, sealing and welding, then putting the steel sheath subjected to degassing and sealing into hot isostatic pressing equipment for reaction, wherein the heating rate is 1-5 ℃/min, the temperature is increased to 800-900 ℃, the pressure is 100-300 MPa, the constant temperature and the pressure are maintained for 3-8 h, and then, the steel sheath is cooled along with a furnace.
Further, the post-treatment sequentially comprises silver coating, punching, oxidation and cleaning.
According to another aspect of the invention, a rare earth oxide modified AgSnO is provided2In2O3The electric contact composite material adopts the rare earth oxide modified AgSnO2In2O3The electric contact composite material is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the in-situ mechanochemical method adopted by the invention promotes the mutual shearing, collision and distortion behaviors between the rare earth oxide and the AgSnIn powder in the reaction process, generates alloying phenomena such as solid solution, bonding and the like, increases the dislocation density and pinning effect of the modified AgSnIn electric contact material, and promotes the formation of high-strength metallurgical bonding between the rare earth oxide reinforced phase particles and the AgSnIn phase.
2. The hot isostatic pressing technology enhances the sintering driving force of the composite powder under the action of high temperature and high pressure, and can further improve the structural compactness of the rare earth oxide modified AgSnIn ingot. Modified AgSnO under the combined action of solid solution bonding and hot isostatic pressing of an in-situ mechanochemical method at high temperature and high pressure2In2O3The electric contact material constructs a special structure with solid solution particles distributed at the front end of the hierarchical dendritic crystal structure in the reaction process, and the special structure is used as a structural channel, so that the transfer of electric arc heat energy can be realized, the temperature rise of the electric contact material can be effectively improved, the electric circulation capability of the material can be improved, and the service life of the material can be prolonged.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows rare earth oxide modified AgSnO in an embodiment of the invention2In2O3A schematic flow diagram of a method of making an electrical contact composite;
FIG. 2 shows rare earth oxide modified AgS according to an embodiment of the present inventionnO2In2O3SEM photograph of the electrical contact composite.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The prior art has achieved some achievements in the aspects of introducing a micro-component formula, a preparation process and the like, and if the micro-component is introduced and the precise regulation and control of a microstructure are added, the method is probably an effective means for preparing a novel modified electric contact material with more excellent electric contact performance.
Therefore, the embodiment of the invention provides rare earth oxide modified AgSnO2In2O3Method for producing an electrical contact composite, AgSnO, in the description of the invention2In2O3Representative of silver tin oxide indium oxide, referring to fig. 1, the method comprises:
s1, preparing AgSnIn alloy atomized powder.
Specifically, the preparation of the AgSnIn alloy atomized powder comprises the following steps: the method comprises the following steps of preparing AgSnIn alloy atomized powder by using Ag, Sn and In as raw materials and utilizing a supersonic speed spray granulation mode, wherein the purities of the Ag, the Sn and the In are all 99.99%. Further, the preparation of the AgSnIn alloy atomized powder by using a supersonic speed spray granulation mode comprises the following steps: in the spraying process, the atomizing medium is nitrogen, double-side ventilation is carried out, the atomizing pressure is 0.3-0.8 MPa, and the alloy superheat degree is 100-250 ℃; and collecting powder after the powder atomization is finished, and sieving the powder by a sieve of 100-300 meshes to obtain AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
S2, preparing rare earth oxide modified AgSnIn composite powder by taking AgSnIn alloy atomized powder as a raw material and rare earth oxide as a modifier and adopting a mechanochemical reaction method.
The material plasticity is poor due to the content of the rare earth oxide is too high, and the modification effect is not obvious due to the content of the rare earth oxide is too low, and in some preferred embodiments, the rare earth oxide is used as a modifier, and comprises: the content of the rare earth oxide accounts for 1.2-4.5 wt% of the total mass of the rare earth oxide and the AgSnIn alloy atomized powder.
In some preferred embodiments, rare earth oxides, such as La2O3、Bi2O3、CeO2And Y2O3And the like, of course, in other embodiments, other rare earth oxides that can regulate and modify the properties of the silver tin oxide can also be used as modifiers, as long as the same function as in the present embodiment can be achieved.
The mechanochemical reaction method in the embodiment is an in-situ mechanochemical reaction method, and specifically, the method for preparing rare earth oxide modified AgSnIn composite powder by adopting the mechanochemical reaction method comprises the following steps: the method comprises the steps of forming total powder by using rare earth oxide and AgSnIn alloy atomized powder, weighing stainless steel grinding balls according to the mass ratio of the stainless steel grinding balls to the total powder of 5-10: 1, and weighing absolute ethyl alcohol according to the mass ratio of the absolute ethyl alcohol to the total powder of 2:1, wherein the absolute ethyl alcohol is a process control agent and plays a role in preventing AgSnIn from being oxidized, dispersing the powder and preventing agglomeration; and sequentially putting the rare earth oxide, the AgSnIn alloy atomized powder, the stainless steel grinding balls and the absolute ethyl alcohol into a ball-milling tank, and grinding for 10-25 h under the condition that the ball-milling rotating speed is 150-350 rpm.
In some preferred embodiments, the ball milling tank is made of stainless steel; the stainless steel grinding ball comprises
A ball,
Ball and stomach regulating
The ball is a ball with a ball-shaped inner surface,
a ball,
A ball,
The weight ratio of the balls is 1:1:1, and the grinding balls with small diameters can fill gaps of the grinding balls with large diameters, so that the grinding effect can be effectively improved.
Of course, in some other embodiments, the material of the ball milling pot may be agate or other materials as long as the same function as in the present embodiment can be achieved.
S3, placing the rare earth oxide modified AgSnIn composite powder in hot isostatic pressing equipment for reaction to obtain a rare earth oxide modified AgSnIn ingot blank.
Specifically, the rare earth oxide modified AgSnIn composite powder is placed in hot isostatic pressing equipment for reaction, and the reaction comprises the following steps: and (2) filling the rare earth oxide modified AgSnIn composite powder into a steel sheath, degassing, sealing and welding, then putting the steel sheath subjected to degassing and sealing into a hot isostatic pressing machine for reaction, wherein the heating rate is 1-5 ℃/min, the temperature is increased to 800-900 ℃, the pressure is 100-300 MPa, the constant temperature and the pressure are maintained for 3-8 h, and then, the steel sheath is cooled along with the furnace.
S4, carrying out hot extrusion on the rare earth oxide modified AgSnIn ingot blank to obtain an AgSnIn-rare earth oxide plate, and carrying out post-treatment to obtain the rare earth oxide modified AgSnO2In2O3An electrical contact material.
Further, the post-treatment sequentially comprises silver coating, punching, oxidation and cleaning.
Correspondingly, the embodiment of the invention also provides rare earth oxide modified AgSnO2In2O3The electric contact composite material adopts the rare earth oxide modified AgSnO2In2O3The preparation method of the electric contact composite material is as shown in figure 2, and the SEM (scanning electron microscope) photograph schematic diagram of the material is shown in figure.
As can be seen from FIG. 2, the prepared rare earth oxide modified AgSnO2In2O3The electric contact material has a special structure in which solid solution particle phase is distributed at the front end of the graded dendrite, wherein the solid solution particle phase is a particle formed by ball-milling a particle of rare earth oxide at the early stage and a dislocation increased by rare earth modification and an oxide cross point formed by oxidation at the later stage. The hierarchical dendritic crystal structure is formed by forming a large amount of dislocation after rare earth modification, increasing an oxygen channel In an oxidation process, and because O, Sn and In are diffused simultaneously, a large amount of Sn and In are oxidized In the channel, thereby forming the hierarchical dendritic crystal structure. Because these two kinds of structures are all perpendicular to the working face, especially hierarchical dendritic structure, in other words, hierarchical dendritic structure is parallel to the current direction, forms the current structure passageway, can effectively reduce electron scattering, simultaneously, when the electric arc was used, also had the effect similar to the lightning rod, can effectively disperse electric arc energy. Therefore, the special structure is used as a structural channel, the transfer of electric arc heat energy can be realized, the temperature rise of the electric contact material is effectively improved, the electric circulation capacity of the material can be improved, and the service life of the material is prolonged.
The invention utilizes spray granulation, an in-situ mechanochemical method and a Hot Isostatic Pressing (HIP) technology to carry out alloy oxidation, thereby preparing the rare earth oxide modified AgSnO2In2O3An electrical contact material. The in-situ mechanochemical method adopted by the invention promotes the mutual shearing, collision and distortion behaviors between the rare earth oxide and the AgSnIn powder in the reaction process, generates alloying phenomena such as solid solution, bonding and the like, increases the dislocation density and pinning effect of the modified AgSnIn electric contact material, and promotes the formation of high-strength metallurgical bonding between the rare earth oxide reinforced phase particles and the AgSnIn phase.
The hot isostatic pressing technology enhances the sintering driving force of the composite powder under the action of high temperature and high pressure, and can further improve the compactness of the rare earth oxide modified AgSnIn ingot blank structure. Modified AgSnO under the combined action of solid solution bonding and hot isostatic pressing of an in-situ mechanochemical method at high temperature and high pressure2In2O3The electric contact material constructs a special structure with solid solution particle phase distributed at the front end of the hierarchical dendritic crystal structure in the reaction process as a structural channel, and can realize electric arc heatThe energy transfer effectively improves the temperature rise of the electric contact material, thereby improving the electric circulation capability of the material and prolonging the service life of the material.
The product particles prepared by the method also modify the graded dendritic crystal structure, and have the functions of dispersing electric arc energy and providing a rapid channel for heat diffusion, so that the temperature rise effect of the contact surface of the electric contact material is improved, the service cycle of the electric service life is prolonged, and the preparation process condition of the whole material is simple and easy for industrialized batch synthesis.
The following rare earth oxide-modified AgSnO for the present invention2In2O3The electrical contact composite material and the method for preparing the same are explained in more detail using examples and comparative examples.
Example 1
S1, preparing AgSnIn alloy atomized powder by using pure Ag (99.99%), Sn (99.99%) and In (99.99%) as raw materials and using a supersonic spray granulation technology, wherein an atomizing medium is nitrogen, double-side ventilation is carried out, the atomizing pressure is 0.3MPa, and the alloy superheat degree is 100 ℃; and after the powder atomization is finished, collecting the powder in the bottom container of the atomization tower and the powder collector, and sieving the powder by using a 200-mesh stainless steel sieve to obtain the AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
S2, taking the AgSnIn alloy atomized powder prepared in the step S1 as a raw material, and taking rare earth oxide La2O3As modifier, La2O3Has an average particle diameter of 3 to 5 μm, and La introduced2O3The content of the modifier is La2O31.2 wt.% of the total mass of the modifier and the AgSnIn alloy atomized powder; preparing La by mechanochemical reaction method2O3Modified AgSnO2In2O3The ball milling tank is made of stainless steel; in stainless steel grinding ball
A ball,
A ball,
The mass ratio of the balls is 1:1: 1; weighing stainless steel grinding balls according to the mass ratio of the stainless steel grinding balls to the total powder of 5: 1; weighing absolute ethyl alcohol according to the mass ratio of the absolute ethyl alcohol to the total powder of 2: 1; la2O3Sequentially putting the powder, AgSnIn alloy atomized powder, stainless steel grinding balls and absolute ethyl alcohol into a stainless steel ball milling tank, and grinding for 25 hours under the condition that the ball milling rotating speed is 150rpm to prepare La with uniform particle size distribution2O3Modified AgSnO2In2O3And (3) composite powder.
S3, mixing the La2O3Modified AgSnO2In2O3Loading the composite powder into a No. 20 steel sheath, degassing, sealing, welding, reacting in hot isostatic pressing equipment at a temperature rise rate of 5 ℃/min to 800 ℃, keeping the pressure at 300MPa, keeping the temperature for 8h, and furnace cooling to obtain La2O3And (3) modifying the AgSnIn ingot blank.
S4, subjecting La obtained after hot isostatic pressing2O3Extruding, silver coating, punching, oxidizing and cleaning the modified AgSnIn ingot blank to obtain La2O3Modified AgSnO2In2O3An electrical contact material.
Example 2
S1, taking pure Ag (99.99%), Sn (99.99%) and In (99.99%) as raw materials, carrying out double-side ventilation by using a supersonic spray granulation technology with an atomizing medium of nitrogen, wherein the atomizing pressure is 0.8MPa, and the alloy superheat degree is 100 ℃; and after the powder atomization is finished, collecting the powder in the bottom container of the atomization tower and the powder collector, and sieving the powder by using a 100-mesh stainless steel sieve to obtain the AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
S2, taking the AgSnIn alloy atomized powder prepared in the step S1 as a raw material and taking rare earth oxide Bi2O3As modifier, Bi2O3Has an average particle diameter of 4 to 7 μm, and Bi is introduced2O3The content of the modifier is Bi2O34.5 percent of the total mass of the modifier and the AgSnIn alloy atomized powder,bi is prepared by mechanochemical reaction method2O3Modified AgSnO2In2O3Composite powder; wherein the ball milling tank is made of stainless steel; in stainless steel grinding ball
A ball,
A ball,
The mass ratio of the balls is 1:1: 1; weighing stainless steel grinding balls according to the mass ratio of the stainless steel grinding balls to the total powder of 10:1, and weighing absolute ethyl alcohol according to the mass ratio of the absolute ethyl alcohol to the total powder of 2: 1; adding Bi2O3Sequentially putting the powder, AgSnIn alloy atomized powder, stainless steel grinding balls and absolute ethyl alcohol into a stainless steel ball-milling tank, and grinding for 10 hours under the condition that the ball-milling rotating speed is 350rpm to prepare Bi with uniform particle size distribution2O3Modified AgSnO2In2O3And (3) composite powder.
S3, mixing Bi2O3Modified AgSnO2In2O3The composite powder is filled into a No. 20 steel sheath for degassing and sealing welding, then the steel sheath after degassing and sealing welding is put into a hot isostatic pressing machine for reaction, the heating rate is 3 ℃/min, the temperature is increased to 900 ℃, the pressure is maintained at 100MPa, the temperature and the pressure are maintained for 3h, and then the steel sheath is cooled along with a furnace to obtain Bi2O3And (3) modifying the AgSnIn ingot blank.
S4 preparation of Bi by hot isostatic pressing2O3Extruding, silver coating, punching, oxidizing and cleaning the modified AgSnIn ingot blank to obtain Bi2O3Modified AgSnO2In2O3An electrical contact material.
Example 3
S1, preparing AgSnIn alloy atomized powder by using pure Ag (99.99%), Sn (99.99%) and In (99.99%) as raw materials and using a supersonic spray granulation technology, wherein an atomizing medium is nitrogen, double-side ventilation is carried out, the atomizing pressure is 0.5MPa, and the alloy superheat degree is 200 ℃; and after the powder atomization is finished, collecting the powder in the bottom container of the atomization tower and the powder collector, and sieving the powder by using a 300-mesh stainless steel sieve to obtain the AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
S2, taking the AgSnIn alloy atomized powder prepared in the step S1 as a raw material and taking rare earth oxide Y2O3And CeO2As a modifier, Y2O3And CeO2The average particle diameter of (2) is 5 to 8 μm; introduced CeO2And Y2O3The content of the modifier accounts for 2.5 percent of the total mass of the powder; preparation of Y by mechanochemical reaction2O3-CeO2Modified AgSnO2In2O3The composite powder is characterized in that the ball milling tank is made of agate; in stainless steel grinding ball
A ball,
A ball,
The mass ratio of the balls is 1:1: 1; weighing stainless steel grinding balls according to the mass ratio of the stainless steel grinding balls to the total powder of 8:1, and weighing absolute ethyl alcohol according to the mass ratio of the absolute ethyl alcohol to the total powder of 2: 1; will Y2O3And CeO2The modifier, the AgSnIn alloy atomized powder, the stainless steel grinding balls and the alcohol are sequentially put into a stainless steel ball milling tank and ground for 14 hours under the condition of the ball milling rotating speed of 250rpm to prepare Y with uniform particle size distribution2O3-CeO2Modified AgSnO2In2O3And (3) composite powder.
S3, mixing Y2O3-CeO2Modified AgSnO2In2O3The composite powder is filled into a No. 20 steel sheath for degassing and sealing welding, then the steel sheath after degassing and sealing welding is put into a hot isostatic pressing machine for reaction, the heating rate is 1 ℃/min, the temperature is increased to 840 ℃, the pressure is kept at 180MPa, the constant temperature and the pressure are kept for 6h, then the steel sheath is cooled along with a furnace,to obtain Y2O3-CeO2And (3) modifying the AgSnIn ingot blank.
S5, hot isostatic pressing Y2O3-CeO2Extruding, silver coating, punching, oxidizing and cleaning the modified AgSnIn ingot blank to obtain Y2O3-CeO2Modified AgSnO2In2O3An electrical contact material.
Comparative example
S1, preparing AgSnIn alloy atomized powder by using pure Ag (99.99%), Sn (99.99%) and In (99.99%) as raw materials and using a supersonic spray granulation technology, wherein an atomizing medium is nitrogen, double-side ventilation is carried out, the atomizing pressure is 0.5MPa, and the alloy superheat degree is 200 ℃; and after the powder atomization is finished, collecting the powder in the bottom container of the atomization tower and the powder collector, and sieving the powder by using a 100-mesh stainless steel sieve to obtain the AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
S2, filling the sieved AgSnIn alloy atomized powder into a No. 20 steel sheath, degassing and sealing, then putting the steel sheath subjected to degassing and sealing into a hot isostatic pressing machine for reaction, heating to 840 ℃ at the heating rate of 3 ℃/min, maintaining the pressure at 180MPa for 6h at constant temperature, and then cooling along with the furnace to obtain an AgSnIn ingot blank.
S3, extruding, silver coating, punching, oxidizing and cleaning the AgSnIn ingot blank obtained after hot isostatic pressing to obtain pure AgSnO2In2O3An electrical contact material.
The rare earth oxide prepared in examples 1 to 3 was modified with AgSnO2In2O3 sample of electrical contact material, and pure AgSnO prepared by comparative example2In2O3The electrical contact material was subjected to the evaluation of electrical life properties, and the detailed results are shown in table 1.
Comparison of Table 1 shows that examples 1-3 have significant advantages in cycle life performance over the blank control, particularly Y in the examples2O3-CeO2Modified AgSnO2In2O3The electrical contact composite performs best.
As can be seen from Table 1, the rare earth oxide is introduced by sprayingThe grain, the in-situ mechanochemical method and the hot isostatic pressing technology have respective technical advantages to prepare the high-performance rare earth oxide modified AgSnO with long cycle life2In2O3Electrically contacting the composite material.
TABLE 1 rare earth oxide modified AgSnO2In2O3Electrical contact performance of electrical contact composites
Claims (10)
1. Rare earth oxide modified AgSnO2In2O3The preparation method of the electric contact composite material is characterized by comprising the following steps:
preparing AgSnIn alloy atomized powder;
preparing rare earth oxide modified AgSnIn composite powder by taking the AgSnIn alloy atomized powder as a raw material and rare earth oxide as a modifier by adopting a mechanochemical reaction method;
placing the rare earth oxide modified AgSnIn composite powder in hot isostatic pressing equipment for reaction to obtain a rare earth oxide modified AgSnIn ingot blank;
hot-extruding the rare earth oxide modified AgSnIn ingot blank into an AgSnIn-rare earth oxide plate, and carrying out post-treatment to obtain the rare earth oxide modified AgSnO2In2O3An electrical contact material.
2. The rare earth oxide modified AgSnO of claim 12In2O3The preparation method of the electric contact composite material is characterized in that the preparation of AgSnIn alloy atomized powder comprises the following steps: the method comprises the following steps of preparing AgSnIn alloy atomized powder by using Ag, Sn and In as raw materials and utilizing a supersonic speed spray granulation mode, wherein the purities of the Ag, the Sn and the In are all 99.99%.
3. The rare earth oxide modified AgSnO of claim 22In2O3Electrical contact laminationThe preparation method of the material is characterized in that the AgSnIn alloy atomized powder prepared by a supersonic speed spray granulation mode comprises the following steps: in the spraying process, the atomizing medium is nitrogen, double-side ventilation is carried out, the atomizing pressure is 0.3-0.8 MPa, and the alloy superheat degree is 100-250 ℃; and collecting powder after the powder atomization is finished, and sieving the powder by a sieve of 100-300 meshes to obtain AgSnIn alloy atomized powder with good sphericity and narrow particle size distribution.
4. The rare earth oxide modified AgSnO of claim 12In2O3The preparation method of the electric contact composite material is characterized in that the method takes the rare earth oxide as a modifier and comprises the following steps: the content of the rare earth oxide accounts for 1.2-4.5 wt% of the total mass of the rare earth oxide and the AgSnIn alloy atomized powder.
5. The rare earth oxide modified AgSnO of claim 42In2O3The preparation method of the electric contact composite material is characterized in that the rare earth oxide is La2O3、Bi2O3、CeO2And Y2O3At least one of (1).
6. The rare earth oxide modified AgSnO of claim 42In2O3The preparation method of the electric contact composite material is characterized in that the preparation method of the rare earth oxide modified AgSnIn composite powder by adopting a mechanochemical reaction method comprises the following steps: forming total powder by using rare earth oxide and AgSnIn alloy atomized powder, weighing stainless steel grinding balls according to the mass ratio of the stainless steel grinding balls to the total powder of 5-10: 1, and weighing absolute ethyl alcohol according to the mass ratio of the absolute ethyl alcohol to the total powder of 2: 1; and sequentially putting the rare earth oxide, the AgSnIn alloy atomized powder, the stainless steel grinding balls and the absolute ethyl alcohol into a ball-milling tank, and grinding for 10-25 h under the condition that the ball-milling rotating speed is 150-350 rpm.
7. The rare earth oxide modified AgSnO of claim 62In2O3The preparation method of the electric contact composite material is characterized in that the material of the ball milling tank is stainless steel or agate; the stainless steel grinding ball comprises
A ball,
Ball and stomach regulating
A ball of
Ball, the
Ball, the
The weight ratio of the balls is 1:1: 1.
8. The rare earth oxide modified AgSnO of claim 12In2O3The preparation method of the electric contact composite material is characterized in that the rare earth oxide modified AgSnIn composite powder is placed in hot isostatic pressing equipment for reaction, and comprises the following steps: and filling the rare earth oxide modified AgSnIn composite powder into a steel sheath, degassing, sealing and welding, then putting the steel sheath subjected to degassing and sealing into hot isostatic pressing equipment for reaction, wherein the heating rate is 1-5 ℃/min, the temperature is increased to 800-900 ℃, the pressure is 100-300 MPa, the constant temperature and the pressure are maintained for 3-8 h, and then, the steel sheath is cooled along with a furnace.
9. The rare earth oxide modified AgSnO of claim 12In2O3The preparation method of the electric contact composite material is characterized in that the post-treatment sequentially comprises silver coating, punching, oxidation and cleaning。
10. Rare earth oxide modified AgSnO2In2O3An electrical contact composite material, characterized in that the rare earth oxide modified AgSnO according to any one of claims 1 to 9 is used2In2O3The electric contact composite material is prepared by the preparation method.
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