CN102618773B - Method for preparing Ag/La1-xSrxCoO3 electric contact composite material - Google Patents
Method for preparing Ag/La1-xSrxCoO3 electric contact composite material Download PDFInfo
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- CN102618773B CN102618773B CN 201210097521 CN201210097521A CN102618773B CN 102618773 B CN102618773 B CN 102618773B CN 201210097521 CN201210097521 CN 201210097521 CN 201210097521 A CN201210097521 A CN 201210097521A CN 102618773 B CN102618773 B CN 102618773B
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- coo
- electric contact
- xsrxcoo3
- composite material
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229910002273 La1–xSrxCoO3 Inorganic materials 0.000 title abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000011858 nanopowder Substances 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 229910018921 CoO 3 Inorganic materials 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 10
- 239000003352 sequestering agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001192 hot extrusion Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 235000012054 meals Nutrition 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000011240 wet gel Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010891 electric arc Methods 0.000 abstract description 3
- 238000002679 ablation Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Powder Metallurgy (AREA)
Abstract
The invention relates to preparation of an electric contact composite material, and aims to provide a method for preparing an Ag/La1-xSrxCoO3 electric contact material. The method includes preparing conductive ceramic micro-nano-powder of an La1-xSrxCoO3 system by a sol-gel method; uniformly mixing the La1-xSrxCoO3 micro-nano-powder and silver powder in a V-shaped powder mixer, and leading the La1-xSrxCoO3 powder to account for 8-20% of the total mass of mixed powder; and isostatically pressing the uniformly mixed powder into a blank, sequentially realizing sintering, re-pressing and re-sintering processes and finally obtaining the Ag/La1-xSrxCoO3 electric contact composite material by means of thermal extrusion forming. The Ag/La1-xSrxCoO3 electric contact composite material is prepared by the sol-gel method, a wild phase La1-xSrxCoO3 in the composite material is nano-level powder, the melt viscosity in micro-molten pools on the surface of the electric contact material under effects of electric arcs can be improved by the high specific surface area of the wild phase, performances including the electric conductivity, the mechanical strength, the abrasion resistance, the electric arc ablation and the like of the electric contact material are comprehensively enhanced, and the problem of difficulty in processing and forming is avoided.
Description
Technical field
The present invention relates to a kind of Novel electrical contact composite manufacture method, specifically, is a kind of Ag/La
1-xSr
xCoO
3The preparation method of electric contact composite material.
Background technology
Contact material and element are core parts and the critical materials of the electronic industry equipment such as power switch, electrical equipment, instrument, are widely used in the every field such as civilian, industrial, military, space flight, aviation, information.Contact material and element are mainly born the effect of connection, breaking circuits and load current, and its performance directly affects reliability service and the life-span of device for switching.Simultaneously, contact material is again the critical material in device for switching, and the salient features of device for switching and the length in life-span are decided by the quality of contact material to a great extent.At present, China's year consume silver-based electric contact material and surpass 10,000,000,000 yuan, and the market requirement maintains sustained and rapid growth.
Up to now, the Ag/CdO material still is considered to the preferred material of electrical contact performance the best.Yet, there is serious environmental problem in the Ag/CdO material, and in February, 2003, European Union promulgated about " some objectionable impurities is used in restriction in electronic electric equipment " (2002/95/EC-RoHS instruction), 2 important instructions of " waste and old electric/electronic device " (2002/96/EC-WEEE instruction).Therefore, new system environment-friendly type contact material is greatly developed in countries in the world, and wherein the most representative have an Ag/SnO
2Material, Ag/ conducting ceramic material etc.China contact material manufacturing enterprise is numerous, but aspect the Ag/SnO2 contact material with also have larger gap abroad, for satisfying national economic development demand, the new system environmental protection electric contact material of high comprehensive performance is demanded exploitation urgently.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and a kind of preparation method of novel Ag/La1-xSrxCoO3 electric contact composite material is provided.
Be the technical solution problem, solution of the present invention is:
A kind of Ag/La is provided
1-xSr
xCoO
3The preparation method of electric contact composite material specifically comprises the steps:
(1) adopt sol-gel method to prepare La
1-xSr
xCoO
3System conductivity ceramics micro nano powder;
(2) with above-mentioned La
1-xSr
xCoO
3Micro nano powder and silver powder mix in the V-type meal mixer, La
1-xSr
xCoO
3Powder accounts for 8%～20% of mixed powder total mass;
(3) powder after mixing is by waiting static pressure to be pressed into base substrate, then successively through oversintering, press again, resintering technique, last hot extrusion molding obtains Ag/La
1-xSr
xCoO
3Electric contact composite material.
2, Ag/La according to claim 1
1-xSr
xCoO
3The preparation method of electric contact composite material is characterized in that,
In step (1), the sol-gel method that adopts prepares La
1-xSr
xCoO
3The method of system conductivity ceramics micro nano powder is: with La (NO
3)
3, Sr (NO
3)
2, Co (NO
3)
26H
2O dissolves in deionized water by stoichiometric ratio, adds appropriate citric acid to make sequestrant under fully stirring, and with ammoniacal liquor or quadrol regulator solution pH value to 6～10, is conducive to form colloidal sol.Water bath heat preservation by certain temperature in still aging process, form wet gel after evaporating unnecessary solvent, then obtain xerogel at 120 ℃ of dry 12h, 600 ℃～800 ℃ sintering in air or oxygen atmosphere, 1～10 ℃/min of temperature rise rate, insulation 2～6h can obtain black La
1-xSr
xCoO
3Nano-powder.
Wherein, La
1-xSr
xCoO
3In conductivity ceramics, the value of X is 0.1～0.9, and in sequestrant Citric Acid Dosage and colloidal sol, the ratio N/J of the total amount of metal ion is 1: 1～2: 1, and the bath temperature in ageing process is 30 ℃～90 ℃, the La that obtains at last
1-xSr
xCoO
3After powder disperses, single particle diameter is 20～50nm, and the macrobead particle diameter of reunion is 50～500nm.
In the present invention, described in step (2) in blending processes of powders, La
1-xSr
xCoO
3The particle size range of powder is 50～500nm, and the particle size range of silver powder is 0.01～50 μ m, mixed powder time 1～6h;
In the present invention, wait static pressure pressure range 100～500MPa described in step (3);
In the present invention, sintering process described in step (3) refers to sintering under the argon gas atmosphere protection, 700～900 ℃ of sintering temperatures, sintering time 2～10h;
In the present invention, described in step (3), multiple compression technology, be to carry out hot pressing under 500～800 ℃, pressure range 300～800MPa, insulation (pressure) time 10～90min;
In the present invention, resintering technique described in step (3) refers under hydrogen atmosphere protection sintering again, 700～900 ℃ of sintering temperatures, sintering time 2～10h;
In the present invention, described in step (3) in hot extrusion molding technique, 300～800 ℃ of mold preheating temperatures, 300～800 ℃ of blank temperatures, the extrusion ratio scope is 10～100, extrusion speed is 1～10cm/min.
With existing Ag/SnO
2Electric contact composite material is compared, and the invention has the beneficial effects as follows:
Make Ag/La by sol-gel method
1-xSr
xCoO
3Wild phase La in electric contact composite material
1-xSr
xCoO
3Be nanoscale powder, its high-ratio surface activity can be improved the melt viscosity in little molten bath, contact material surface under arcing, the performances such as the specific conductivity of comprehensive raising contact material, physical strength, wear resistance, anti-electric-arc ablation, there is not the problem of processing, difficult forming in the while.
La
1-xSr
xCoO
3Belong to the serial high-temperature superconductivity ceramics of perovskite structure, the room temperature resistivity of having reported is low to moderate 10
-5Ω cm magnitude is with the resistivity (10 of contact material
-6Ω cm magnitude) close.And the resistivity of SnO2 is 93 Ω cm, by experiment, and Ag/La
1-xSr
xCoO
3The electrical contact performance of material is better than Ag/SnO
2
The present invention is carried silver-colored technology at La by the surface
1-xSr
xCoO
3The surface covers silver layer in advance, has improved the wettability of wild phase and silver matrix; Guarantee Ag/La
1-xSr
xCoO
3Contact material is subjected to the arc erosion rear surface serious La can not occur
1-xSr
xCoO
3Segregation be the more important thing is La
1-xSr
xCoO
3Wild phase can decompose near Ag fusing point (960 ℃) in advance, thereby makes Ag/La
1-xSr
xCoO
3Serviceability be similar to Ag/CdO, have significant arc blow-out, arc extinguishing effect when electric arc occurs, extend the work-ing life of material.
The present invention is by selecting the wild phase material La of high comprehensive performance
1-xSr
xCoO
3, not only improved the volume of wild phase in the electric contact composite material, also expanded the electric life of contact material.Generally speaking, compare Ag/SnO
2Material, Ag/La
1-xSr
xCoO
3Can economize on silver 3%～8%.
Embodiment
Below the present invention is further described by example.
The preparation method of Ag/La1-xSrxCoO3 electric contact composite material provided by the invention specifically comprises the steps:
(1) adopt sol-gel method to prepare La
1-xSr
xCoO
3System conductivity ceramics micro nano powder;
(2) with above-mentioned La
1-xSr
xCoO
3Micro nano powder and silver powder mix in the V-type meal mixer, La
1-xSr
xCoO
3Powder accounts for 8%～20% of mixed powder total mass;
(3) powder after mixing is by waiting static pressure to be pressed into base substrate, then successively through oversintering, press again, resintering technique, last hot extrusion molding obtains Ag/La
1-xSr
xCoO
3Electric contact composite material.
In step (1), the sol-gel method that adopts prepares La
1-xSr
xCoO
3The method of system conductivity ceramics micro nano powder is: with La (NO
3)
3, Sr (NO
3)
2, Co (NO
3)
26H
2O dissolves in deionized water by stoichiometric ratio, adds appropriate citric acid to make sequestrant under fully stirring, and with ammoniacal liquor or quadrol regulator solution pH value to 6～10, is conducive to form colloidal sol.Water bath heat preservation by certain temperature in still aging process, form wet gel after evaporating unnecessary solvent, then obtain xerogel at 120 ℃ of dry 12h, 600 ℃～800 ℃ sintering in air or oxygen atmosphere, 1～10 ℃/min of temperature rise rate, insulation 2～6h can obtain black La
1-xSr
xCoO
3Nano-powder.Wherein, La
1-xSr
xCoO
3In conductivity ceramics, the value of X is 0.1～0.9, and in sequestrant Citric Acid Dosage and colloidal sol, the ratio N/J of the total amount of metal ion is 1: 1～2: 1, and the bath temperature in ageing process is 30 ℃～90 ℃, the La that obtains at last
1-xSr
xCoO
3After powder disperses, single particle diameter is 20～50nm, and the macrobead particle diameter of reunion is 50～500nm.
Testing data in each embodiment sees the following form:
At last, it is also to be noted that, what more than enumerate is only part specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those skilled in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. Ag/La
1-xSr
xCoO
3The preparation method of electric contact composite material specifically comprises the steps:
(1) adopt sol-gel method to prepare La
1-xSr
xCoO
3System conductivity ceramics micro nano powder;
(2) with above-mentioned La
1-xSr
xCoO
3Micro nano powder and silver powder mix in the V-type meal mixer, La
1-xSr
xCoO
3Powder accounts for 8%～20% of mixed powder total mass;
(3) powder after mixing is by waiting static pressure to be pressed into base substrate, then successively through oversintering, press again, resintering technique, last hot extrusion molding obtains Ag/La
1-xSr
xCoO
3Electric contact composite material;
The concrete steps of step (1) are: with La (NO
3)
3, Sr (NO
3)
2, Co (NO
3)
26H
2O dissolves in deionized water by stoichiometric ratio, adds citric acid to make sequestrant under fully stirring, and with ammoniacal liquor or quadrol regulator solution pH value to 6～10, is conducive to form colloidal sol; Water bath heat preservation by 30 ℃～90 ℃ in still aging process, form wet gel after evaporating unnecessary solvent, then obtain xerogel at 120 ℃ of dry 12h, 600 ℃～800 ℃ sintering in air or oxygen atmosphere, 1～10 ℃/min of temperature rise rate, insulation 2～6h can obtain black La
1-xSr
xCoO
3Nano-powder;
Wherein, La
1-xSr
xCoO
3In conductivity ceramics, the value of X is 0.1～0.9, and in sequestrant Citric Acid Dosage and colloidal sol, the ratio N/J of the total amount of metal ion is 1: 1 ~ 2: 1;
In step (3), the described static pressure pressure range 100～500MPa that waits; Sintering process refers to sintering under the argon gas atmosphere protection, 700～900 ℃ of sintering temperatures, sintering time 2～10h; Multiple compression technology is to carry out hot pressing under 500～800 ℃, pressure range 300～800MPa, soaking time 10～90min; Resintering technique refers under hydrogen atmosphere protection sintering again, 700～900 ℃ of sintering temperatures, sintering time 2～10h; In hot extrusion molding technique, 300～800 ℃ of mold preheating temperatures, 300～800 ℃ of blank temperatures, the extrusion ratio scope is 10～100, extrusion speed is 1～10cm/min.
2. Ag/La according to claim 1
1-xSr
xCoO
3The preparation method of electric contact composite material is characterized in that, the La that obtains at last
1-xSr
xCoO
3Single particle diameter after powder disperses is 20～50nm, and the macrobead particle diameter of reunion is 50 ~ 500nm.
3. Ag/La according to claim 1
1-xSr
xCoO
3The preparation method of electric contact composite material is characterized in that, described in step (2) in blending processes of powders, and La
1-xSr
xCoO
3The particle size range of powder is 50 ~ 500nm, and the particle size range of silver powder is 0.01～50 μ m, mixed powder time 1～6h.
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|---|---|---|---|
| CN 201210097521 CN102618773B (en) | 2012-04-05 | 2012-04-05 | Method for preparing Ag/La1-xSrxCoO3 electric contact composite material |
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|---|---|---|---|
| CN 201210097521 CN102618773B (en) | 2012-04-05 | 2012-04-05 | Method for preparing Ag/La1-xSrxCoO3 electric contact composite material |
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| CN102618773B true CN102618773B (en) | 2013-06-19 |
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| CN104741602B (en) * | 2013-12-31 | 2017-09-15 | 施耐德电器工业公司 | A kind of electrical contact material including metal and metal oxide and preparation method thereof |
| CN104894421B (en) * | 2015-05-04 | 2017-01-11 | 浙江大学 | Preparation method of novel Ag-based lanthanum stannate composite electric contact material |
| CN106098421A (en) * | 2016-08-05 | 2016-11-09 | 雷春生 | A kind of compound electric apparatus contact material of strong electric property and preparation method thereof |
| CN106636723B (en) * | 2016-12-30 | 2018-04-20 | 衢州学院 | One kind is with La1‑xSrxInO3Microballoon is the Ag base electrical contact material preparation methods of enhancing phase |
| CN107574333B (en) * | 2017-08-10 | 2019-05-21 | 浙江大学 | A kind of preparation method of Ag-YAG contact material |
| CN111636005B (en) * | 2020-04-21 | 2021-11-30 | 东北大学 | Preparation method of silver conductive ceramic electrical contact material |
| CN112209428B (en) * | 2020-09-14 | 2022-07-01 | 浙江工业大学 | Spherical La2CuSnO6Complex phase ceramic powder and preparation method and application thereof |
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| DE19903619C1 (en) * | 1999-01-29 | 2000-06-08 | Louis Renner Gmbh | Powder metallurgical composite material, especially for high voltage vacuum switch contacts, comprises refractory solid solution or intermetallic phase grains embedded in a metal matrix |
| CN1180105C (en) * | 2002-02-09 | 2004-12-15 | 贵研铂业股份有限公司 | Silver-base electric contact composite material |
| CN102312150A (en) * | 2011-09-29 | 2012-01-11 | 浙江大学 | Preparation method of Ag / Ti3SiC2 electric contact composite material |
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