CN102522241B - CuCr alloy contact material and preparation method thereof - Google Patents
CuCr alloy contact material and preparation method thereof Download PDFInfo
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- CN102522241B CN102522241B CN201110412822.7A CN201110412822A CN102522241B CN 102522241 B CN102522241 B CN 102522241B CN 201110412822 A CN201110412822 A CN 201110412822A CN 102522241 B CN102522241 B CN 102522241B
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Abstract
本发明公开了一种CuCr合金触头材料及其制备方法。该方法包括如下步骤：(1)采用物理气相沉积在自转的基片上沉积Cu膜；(2)启动Cr组元的沉积，并保持Cr组元的相对沉积速率梯度增长，在所述Cu膜上沉积CuCr合金膜a；所述Cr组元的相对沉积速率为Cr组元的沉积速率与Cu组元的沉积速率的比值，所述Cr组元的沉积速率为单位元面积的所述基片上单位时间内沉积的Cr质量；所述Cu组元的沉积速率为单位元面积的所述基片上单位时间内沉积的Cu质量；(3)保持Cr组元的相对沉积速率不变，在所述CuCr合金膜a上继续沉积CuCr合金膜b，然后在真空条件下经原位退火即得。本发明采用物理气相沉积的方法制备了高强度、高导电、高耐电弧侵蚀的CuCr合金触头材料，同时该方法可以节约能源和原材料的消耗。The invention discloses a CuCr alloy contact material and a preparation method thereof. The method comprises the following steps: (1) adopting physical vapor deposition to deposit a Cu film on a rotating substrate; (2) starting the deposition of Cr components, and keeping the relative deposition rate gradient growth of Cr components, on the Cu film CuCr alloy film a is deposited; the relative deposition rate of the Cr component is the ratio of the deposition rate of the Cr component to the deposition rate of the Cu component, and the deposition rate of the Cr component is the unit on the substrate of the unit cell area. The Cr quality that deposits in time; The deposition rate of described Cu component is the Cu quality that deposits per unit time on the described substrate of unit element area; (3) keep the relative deposition rate of Cr component constant, in described CuCr The CuCr alloy film b is continuously deposited on the alloy film a, and then annealed in situ under vacuum conditions. The invention adopts the method of physical vapor deposition to prepare the CuCr alloy contact material with high strength, high conductivity and high resistance to arc erosion, and meanwhile, the method can save energy and raw material consumption.
Description
Technical field
The present invention relates to a kind of CuCr alloy contact material and preparation method thereof, belong to metal material technical field.
Background technology
The present life of people is increasing to electric degree of dependence, and primary cut-out etc. are most important assemblies in electric power system.Circuit breaker is being undertaken the effect of control and protection electric power system, and wants the safe and reliable operation of energy.Contact is the critical component of generally acknowledged high-voltage switch gears such as circuit breaker, and it directly affects the electric property of vacuum circuit-breaker.Contact material plays decisive role to the development of circuit breaker to a great extent.CuCr alloy material is a kind of good long-life vacuum contact material, is optimal contact material in existing all contact materials, and it has high proof voltage intensity, good resistance to arc erosion, low cut-off current and the good ability of damming.The main method of preparation CuCr alloy contact material has powder sintering, infiltration method, consumable electrode method, arc melting method and induction melting-casting etc. now.These methods will consume a large amount of energy and raw material in the process of preparation, and production cost is higher, and at aspect of performance, conductivity and intensity need further raising.Take powder sintering as example, and it is raw material that the method be take the powder of Cu and Cr, by the abundant mixed material of mechanical agitation, and the CuCr alloy cube matherial preparing, Cr constituent element wherein has larger crystallite dimension, reaches several microns even tens microns.And contact material also will ensure good conductivity when guaranteeing to have good anti electric arc corrosion, therefore in CuCr alloy, Cr constituent element must be distributed among Cu constituent element uniformly, Cu constituent element must be connected simultaneously, so that transmission electronic can transmit smoothly optional position in material, thereby reduce the difference of material diverse location.The density of material is more high better, otherwise stability of contact material, useful life etc. all can have a greatly reduced quality, and is unfavorable for reducing the use cost of contact material.For improving the performance of CuCr alloy contact material, the grain refinement of Cr constituent element is important and effective means.The grain refinement of Cr constituent element is conducive to improve proof voltage intensity, reduces the electric current that dams, and reduces contact material surface roughness, strengthens the resistance to arc erosion of contact material.So powder sintering is difficult to further crystal grain thinning, improve compactness, conductivity, reduce energy consumption and material consumption.At present, the preparation of domestic contact material is seriously limited by external technical monopoly, and crucial contact material is by high price import external product.Therefore no matter technically, still from the consideration of business, all need to study new contact material technology of preparing.
Summary of the invention
The object of this invention is to provide a kind of CuCr alloy contact material and preparation method thereof.
The preparation method of a kind of CuCr alloy contact material provided by the invention, comprises the steps:
(1) adopt physical vapour deposition (PVD) on the substrate of rotation, to deposit Cu film;
(2) adopt physical vapour deposition (PVD), start the deposition of Cr constituent element, and keep the relative deposition rate of Cr constituent element to increase, on described Cu film, deposit CuCr alloy film a; The relative deposition rate of described Cr constituent element is the ratio of the deposition rate of Cr constituent element and the deposition rate of Cu constituent element, the Cr quality of deposition in the unit interval on the described substrate that the deposition rate of described Cr constituent element is unit are; The deposition rate of described Cu constituent element is the Cu quality of deposition in the unit interval on the described substrate of unit are;
(3) adopt physical vapour deposition (PVD), keep the relative deposition rate of Cr constituent element constant, on described CuCr alloy film a, continue deposition CuCr alloy film b, then under vacuum condition, through in-situ annealing, obtain described CuCr alloy contact material.
In above-mentioned preparation method, the thickness of described Cu film can be 500nm～50 μ m, specifically can be 700nm, 1 μ m, 2 μ m or 20 μ m; The thickness of described CuCr alloy film a can be 5 μ m～10cm, specifically can be 5.5 μ m, 6.5 μ m, 27 μ m or 487 μ m; The thickness of described CuCr alloy film b can be 1 μ m～10cm, specifically can be 1 μ m, 2.6 μ m, 5 μ m or 53 μ m.
In above-mentioned preparation method, in step (2), the relative deposition rate of described Cr constituent element can be 0～15, but is not 0, specifically can be 0.02～0.27,0.01～0.25,0.01～1.5 or 0.01～0.08.
In above-mentioned preparation method, in step (3), the relative deposition rate of described Cr constituent element can be 0.01～1.5, specifically can be 0.08,0.25,0.27 or 1.5.
In above-mentioned preparation method, described physical vapour deposition (PVD) specifically can be magnetic control co-sputtering coating method; The vacuum degree of described magnetic control co-sputtering coating method can be 1 * 10
-3pa～7 * 10
-8pa, specifically can be 5 * 10
-5pa, 1 * 10
-5pa or 7 * 10
-4pa, operating air pressure can be 0.05Pa～5Pa, specifically can be 0.4Pa, 0.8Pa or 5Pa; Gas flow can be 5sccm～2000sccm, specifically can be 20sccm, 90sccm or 200sccm, and automatic bias can be 0V～2000V, specifically can be 0V or 1000V; The autorotation speed of described substrate can be 2 turn/min of turn/min～50, specifically can be 20 turn/min, 30 turn/min or 45 turn/min, the diameter of Cu target can be 20mm～1000mm, specifically can be 75mm, the diameter of Cr target can be 20mm～1000mm, specifically can be 75mm, the spacing of Cu target and Cr target and described substrate all can be 5cm～70cm, specifically can be 6cm, 10cm or 15cm.
In above-mentioned preparation method, described physical vapour deposition (PVD) specifically can be vacuum evaporatation; The vacuum degree of described vacuum evaporatation can be 1 * 10
-3pa～7 * 10
-8pa, specifically can be 7 * 10
-8pa, the autorotation speed of described substrate can be 2 turn/min of turn/min～50, specifically can be 4 turn/min, and the spacing of Cu target and Cr target and described substrate all can be 5cm～70cm, specifically can be 70cm.
In above-mentioned preparation method, described substrate can be oxygen-free copper.
In above-mentioned preparation method, described in step (3), the vacuum degree of vacuum condition can be 5 * 10
-2pa～7 * 10
-8pa, specifically can be 3 * 10
-4pa, 5 * 10
-4pa or 1 * 10
-7pa, the temperature of described in-situ annealing can be 300 ℃～600 ℃, specifically can be 300 ℃, 500 ℃ or 600 ℃, the time of described in-situ annealing can be 30min～300min, specifically can be 30min, 90min or 300min, in described in-situ annealing process, Cu grain growth, number of grain boundaries reduces, and can improve conductivity and the compactness of material, make nano level Cr separate out, these nano level Cr are embedded among the Cu constituent element being connected simultaneously; Described in-situ annealing step can make the surface roughness of material lower, reduces the contact resistance between contact in switch contacts, thereby extends the useful life of switch contacts, improves conduction current ability and the usefulness of switch contacts.
The present invention also provides the CuCr being prepared by said method alloy contact material; In described material, Cu and Cr are very even in the distribution of the same depth location of film, and Cu constituent element is connected as a single entity network-like, Cr is distributed among the grid of copper networks, therefore every nature differences such as electrical properties of optional position, alloy firm surface are very little, overall conductivity >=the 20%IACS of contact material, traditional preparation method than CuCr contact material, contact material prepared by the method for physical vapour deposition (PVD), Cr constituent element crystallite dimension can obtain very large refinement, crystallite dimension is less than 400nm, and material compactness is good, relative density >=99%.
The present invention adopts the method for physical vapour deposition (PVD) to prepare the CuCr alloy contact material of high strength, high conduction, high resistance to arc erosion, and the method can energy savings and raw-material consumption simultaneously.
Embodiment
The experimental technique using in following embodiment if no special instructions, is conventional method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, CuCr alloy contact material
On the oxygen-free copper substrate through polishing, adopt magnetic control co-sputtering coating method to deposit, wherein, the base vacuum degree of controlling sputter is 5 * 10
-5pa, the operating air pressure of work atmosphere high-purity Ar gas is 0.4Pa, gas flow is 20sccm, and the speed of controlling substrate rotation is 20 turn/min, Cu target diameter is 75mm, and Cr target diameter is 75mm, two kinds of targets are 15cm to the distance of oxygen-free copper substrate, and automatic bias is 0V; First, the sputtering power of fixation of C u target is that 180W is constant all the time, the pure Cu film of the one deck of growing on oxygen-free copper substrate, and growth time 15min obtains the pure Cu film that thickness is 1 μ m; Then keep the sputtering power of Cu constituent element to continue growth, start the growth of Cr constituent element, the sputtering power of Cr target is started by 10W, every 5min, increase 10W afterwards, with the increase power of thickness, increase to gradually 200W and obtain the CuCr alloy firm a that thickness is 6.5 μ m, in this deposition process, the relative deposition rate of Cr increases to 0.27 by 0.02; Then keep the sputtering power of Cu target 180W and Cr target 200W constant, on CuCr alloy firm a, continued growth 30min obtains the CuCr alloy firm b that thickness is 2.6 μ m; Sputter stops the atmosphere of ventilating after having grown, in vacuum degree 5 * 10
-4under Pa condition, carry out in-situ annealing and process, annealing temperature is 500 ℃, and annealing time is 90min.
The conductance of the CuCr alloy contact material that the present embodiment obtains is 56%IACS, Cr crystallite dimension 60nm, surperficial r.m.s. roughness 35nm, density 99.8%.
The preparation of embodiment 2, CuCr alloy contact material
On the oxygen-free copper substrate through polishing, adopt magnetic control co-sputtering coating method to deposit, wherein, the base vacuum degree of controlling sputter is 1 * 10
-5pa, the operating air pressure of work atmosphere high-purity Ar gas is 0.8Pa, gas flow is 90sccm, and the speed of controlling substrate rotation is 30 turn/min, Cu target diameter is 75mm, and Cr target diameter is 75mm, two kinds of targets are 10cm to the distance of oxygen-free copper substrate, and automatic bias is 1000V; First, the sputtering power of fixation of C u target is that 400W is constant all the time, the pure Cu film of the one deck of growing on oxygen-free copper substrate, and growth time 10min obtains the pure Cu film that thickness is 2 μ m; Then keep the sputtering power of Cu constituent element to continue growth, start the growth of Cr constituent element, the sputtering power of Cr target is started by 10W, every 5min, increase 25W afterwards, with the increase power of thickness, increase to gradually 500W and obtain the CuCr alloy firm a that thickness is 27 μ m, in this deposition process, the relative deposition rate of Cr increases to 0.25 by 0.01; Then keep the sputtering power of Cu target 400W and Cr target 500W constant, on CuCr alloy firm a, continued growth 20min obtains the CuCr alloy firm b that thickness is 5 μ m; Sputter stops the atmosphere of ventilating after having grown, in vacuum degree 3 * 10
-4under Pa condition, carry out in-situ annealing and process, annealing temperature is 600 ℃, and annealing time is 30min.
The conductance of the CuCr alloy contact material that the present embodiment obtains is 50%IACS, Cr crystallite dimension 70nm, surperficial r.m.s. roughness 40nm, density 99.7%.
The preparation of embodiment 3, CuCr alloy contact material
On the oxygen-free copper substrate through polishing, adopt vacuum evaporatation to deposit, mode of heating is electron beam heating, and wherein, the base vacuum degree of controlling plated film is 7 * 10
-8pa, the autorotation speed of substrate is 4 turn/min, Cu target and Cr target are 70cm to the spacing of substrate; First, the heating power 400W of fixation of C u target is constant all the time, the pure Cu film of the one deck of growing on oxygen-free copper substrate, and growth time 30min obtains the pure Cu film that thickness is 700nm; Then the lasting growth that keeps Cu constituent element, start the growth of Cr constituent element, the heating power of Cr target is started by 10W, every 12min, increase 5W afterwards, with the increase power of thickness, increase to gradually 100W and obtain the CuCr alloy firm a that thickness is 5.5 μ m, in this deposition process, the relative deposition rate of Cr increases to 0.08 by 0.01; Then keep the heating power of Cu target 400W and Cr target 100W constant, on CuCr alloy firm a, continue 40min and obtain the CuCr alloy firm b that thickness is 1.0 μ m; Then in vacuum degree, be 1 * 10
-7under Pa condition, carry out in-situ annealing and process, annealing temperature is 300 ℃, and annealing time is 300min.
The conductance of the CuCr alloy contact material that the present embodiment obtains is 75%IACS, Cr crystallite dimension 43nm, surperficial r.m.s. roughness 21nm, density 99.9%.
The preparation of embodiment 4, CuCr alloy contact material
On the oxygen-free copper substrate through polishing, adopt magnetic control co-sputtering coating method to deposit, wherein, the base vacuum degree of controlling sputter is 7 * 10
-4pa, the operating air pressure of work atmosphere high-purity Ar gas is 5Pa, gas flow is 200sccm, and the speed of controlling substrate rotation is 45 turn/min, Cu target diameter is 75mm, and Cr target diameter is 75mm, two kinds of targets are 6cm to the distance of oxygen-free copper substrate, and automatic bias is 0V; First, the sputtering power of fixation of C u target is that 450W is constant all the time, the pure Cu film of the one deck of growing on oxygen-free copper substrate, and growth time 25min obtains the pure Cu film that thickness is 20 μ m; Then keep the sputtering power of Cu constituent element to continue growth, start the growth of Cr constituent element, the sputtering power of Cr target is started by 20W, every 10min, increase 20W afterwards, with the increase power of thickness, increase to gradually 870W and obtain the CuCr alloy firm a that thickness is 487 μ m, in this deposition process, the relative deposition rate of Cr increases to 1.5 by 0.01; Then keep the sputtering power of Cu target 450W and Cr target 870W constant, on CuCr alloy firm a, continued growth 40min obtains the CuCr alloy firm b that thickness is 53 μ m; Sputter stops the atmosphere of ventilating after having grown, in vacuum degree 5 * 10
-4under Pa condition, carry out in-situ annealing and process, annealing temperature is 600 ℃, and annealing time is 300min.
The conductance of the CuCr alloy contact material that the present embodiment obtains is 30%IACS, Cr crystallite dimension 170nm, surperficial r.m.s. roughness 87nm, density 99.2%.
Claims (6)
1. a preparation method for CuCr alloy contact material, comprises the steps:
(1) adopt physical vapour deposition (PVD) on the substrate of rotation, to deposit Cu film;
(2) start the deposition of Cr constituent element, and keep the relative deposition rate gradient of Cr constituent element to increase, on described Cu film, deposit CuCr alloy film a; The relative deposition rate of described Cr constituent element is the ratio of the deposition rate of Cr constituent element and the deposition rate of Cu constituent element, the Cr quality of deposition in the unit interval on the described substrate that the deposition rate of described Cr constituent element is unit are; The deposition rate of described Cu constituent element is the Cu quality of deposition in the unit interval on the described substrate of unit are;
(3) keep the relative deposition rate of Cr constituent element constant, on described CuCr alloy film a, continue deposition CuCr alloy film b, then under vacuum condition, through in-situ annealing, obtain described CuCr alloy contact material;
The thickness of described Cu film is 500nm～50 μ m; The thickness of described CuCr alloy film a is 5 μ m～10cm; The thickness of described CuCr alloy film b is 1 μ m～10cm;
In step (2), the relative deposition rate of described Cr constituent element is 0～15, but is not 0;
In step (3), the relative deposition rate of described Cr constituent element is 0.01～1.5.
2. method according to claim 1, is characterized in that: described in step (1), physical vapour deposition (PVD) is magnetic control co-sputtering coating method; The vacuum degree of described magnetic control co-sputtering coating method is 1 * 10
-3pa～7 * 10
-8pa, operating air pressure is 0.05Pa～5Pa; Gas flow is 5sccm～2000sccm, and automatic bias is 0V～2000V.
3. method according to claim 2, it is characterized in that: in described magnetic control co-sputtering coating method, the autorotation speed of described substrate is 2 turn/min of turn/min～50, the diameter of Cu target is 20mm～1000mm, the diameter of Cr target is 20mm～1000mm, and the spacing of Cu target and Cr target and described substrate is 5cm～70cm.
4. according to arbitrary described method in claim 1-3, it is characterized in that: described in step (1), physical vapour deposition (PVD) is vacuum evaporatation; The vacuum degree of described vacuum evaporatation is 1 * 10
-3pa～7 * 10
-8pa, the autorotation speed of described substrate is 2 turn/min of turn/min～50, the spacing of Cu target and Cr target and described substrate is 5cm～70cm.
5. according to arbitrary described method in claim 1-3, it is characterized in that: described substrate is oxygen-free copper.
6. according to arbitrary described method in claim 1-3, it is characterized in that: described in step (3), the vacuum degree of vacuum condition is 5 * 10
-2pa～7 * 10
-8pa, the temperature of described in-situ annealing is 300 ℃～600 ℃, the time of described in-situ annealing is 30min～300min.
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| CN104103432B (en) * | 2014-07-21 | 2015-11-18 | 南通万德科技有限公司 | Switch contact containing molybdenum alloy coating and preparation method thereof |
| CN104103435B (en) * | 2014-07-21 | 2016-07-13 | 南通万德科技有限公司 | A kind of tungsten alloy switch contact of arc ablation resistance and preparation method thereof |
| CN104894515A (en) * | 2015-05-27 | 2015-09-09 | 陕西斯瑞工业有限责任公司 | Electric-arc ion plating method for forming CuCr coating on surface of CuCr contact |
| CN106086493B (en) * | 2016-08-18 | 2018-02-09 | 江西理工大学 | A kind of method that fast low temperature sintering prepares CuCr alloy materials |
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|---|---|---|---|---|
| CN1807675A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Single-target magnetic control sputtering process for Cu1-xCrx alloy film |
| CN101067170A (en) * | 2007-06-08 | 2007-11-07 | 东北大学 | Method for preparing CuCr alloy contact material by self-propagating melting casting-electroslag remelting |
| CN101696490A (en) * | 2009-11-02 | 2010-04-21 | 河南理工大学 | Method for preparing wearproof electric corrosion-resisting alloy layer on pure copper surface through magnetron sputtering |
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| JP4719170B2 (en) * | 2007-02-28 | 2011-07-06 | 株式会社東芝 | Manufacturing method of contact material for vacuum circuit breaker |
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|---|---|---|---|---|
| CN1807675A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Single-target magnetic control sputtering process for Cu1-xCrx alloy film |
| CN101067170A (en) * | 2007-06-08 | 2007-11-07 | 东北大学 | Method for preparing CuCr alloy contact material by self-propagating melting casting-electroslag remelting |
| CN101696490A (en) * | 2009-11-02 | 2010-04-21 | 河南理工大学 | Method for preparing wearproof electric corrosion-resisting alloy layer on pure copper surface through magnetron sputtering |
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| JP特开2008-212946A 2008.09.18 |
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