CN1265409C - Copper/rare-earth oxide/carbon contact and method for producing same - Google Patents

Abstract

The present invention relates to a copper/ rare earth oxide/carbon contact which is composed of the components of the following proportion by weight: 0.1 to 2.0 of carbon, 0.1 to 15 of ytterbium trioxide or samarium trioxide, 0.05 to 2.0 of alloying metal and copper as the rest. The contact manufactured in a method of powder metallurgy and electroplating deposition has the advantages of high antioxidant ability and high capability of electric arc burning loss resistance.

Description

Copper/rare earth oxide/carbon contact and production method thereof

One, affiliated technical field

The present invention relates to a kind of copper base contact and production method thereof that is used for low-voltage electrical apparatus such as contactor, circuit breaker etc.

Two, background technology

In the low-voltage electrical apparatus field, contact silver-based material commonly used is made, as silver/nickel contact material, silver/oxide contact tip material, silver/carbon contact material etc.But silver-based contact production cost height adds that China is one again and lacks silver-colored big country, and therefore researching and developing copper base contact replacement silver-based contact is a kind of inevitable development trend.At present, the kind of the copper-base contact material of production is a lot, but its limitation is all arranged, and main shortcoming is a little less than the anti-oxidant and arc resistant scaling loss ability, has therefore influenced applying of copper base contact.

Three, summary of the invention

The object of the present invention is to provide a kind of copper/rare earth oxide/carbon contact, its material method production, its oxidation resistance and arc resistant scaling loss ability height of powder metallurgy and electroplating deposition.

For achieving the above object, the solution that the present invention takes is: a kind of copper/rare earth oxide/carbon contact, the composition proportion of its material are (percentage by weight): carbon 0.1～2.0, Dysprosium trioxide or samarium sesquioxide 0.1～15, metal of alloying 0.05～2.0, copper surplus.

Described metal of alloying comprises zirconium, aluminium, cadmium, tin and lanthanum.

Described carbon is diamond or graphite.

Above-mentioned copper/rare earth oxide/carbon contact can be by following method production.

1, galvanoplastic production of copper/rare earth oxide/carbon contact:

(1) preparation of electroplate liquid: take by weighing aequum potassium cyanide and be dissolved in the warm water, take by weighing the aequum cuprous cyanide and slowly add in the potassium cyanide solution under constantly stirring, control adds temperature, makes solution temperature can not be elevated to more than 60 ℃; Taking by weighing aequum potassium hydroxide is dissolved in the distilled water; After the both is dissolved well, miscible mutually, and add water to the regulation liquid level, after stirring, filter, analyze, adjusting, can use;

(2) electroplate:, clean up then the sulfuric acid passivation of the corrosion resistant plate of 0.5～1.0mm; Adding granularity in electroplate liquid is the Dy of 2～4 μ m ₂O ₃Or Sm ₂O ₃With granularity be the C of 0.1～1.5 μ m, use copper alloy plate as anode then, corrosion resistant plate is as negative electrode, cathode-current density is 5～10A/dm ²Electroplate; The electroplating power supply DC power supply or the pulse power, the most handy pulse power, negative electrode is used the plastics mold and is shielded, and solution need stir during plating; Plating bath should be monitored the content of the suspended matter in the plating bath through outside the general plating solution maintenance during plating, regularly replenishes; Electroplating velocity is 100～200 μ m/h, coating is thick 〉=and 0.5mm;

(3) high-temperature process: electroplate sheet material never become rusty take off on the steel plate after, in the protective atmosphere sintering furnace, handle, 930 ℃ of sintering temperatures, protective atmosphere is nitrogen, argon gas, temperature retention time 2～hour;

(4) rolling: as will to carry out cold rolling through the plating sheet material of high-temperature process to required thickness;

(5) blanking: will make corresponding workpiece through the punch press blanking through rolling plating sheet material;

(6) high temperature is handled again: make corresponding workpiece through the punch press blanking and handle in the isostatic sintering stove; 930 ℃ of sintering temperatures, pressure 6～9MPa, protective atmosphere are nitrogen, argon gas; temperature retention time 2～3 hours makes described copper/rare earth oxide/carbon contact.

2, powder metallurgy single stamped method production of copper/rare earth oxide/carbon contact:

(1) mixes powder: with Dy ₂O ₃Or Sm ₂O ₃After in ultrasonic equipment, disperseing with alcohol with C, add in the load weighted 200 order electrolytic copper powders, stir while adding, carry out just mixing, mixing 2 hours in mixed powder machine is then poured out and is carried out wet-milling and cross 100 mesh sieves, add copper alloy powder then, mixed in mixed powder machine 2 hours, and poured out in baking oven after 60～80 ℃ of oven dry, it is standby to cross 80 mesh sieves;

(2) compacting: select suitable mold to be pressed into corresponding workpiece, pressed density is 7.15～7.25g/cm ³

(3) just burn: mixing is loaded on and puts into vacuum-protective atmosphere sintering furnace in the sintering boat and carry out sintering as filler with aluminium oxide powder with workpiece; Carrying out shove charge below 80 ℃, vacuumize vacuum degree≤5 * 10 then ^-3Pa heats up then, programming rate≤10 ℃/min, and intensification limit, limit is evacuated to 300 ℃, be incubated 30 minutes, close vacuum then, charging into Ar is pressure-fired, continue to be warming up to 700 ℃ of insulations 30 minutes, proceed to 970 ℃ of insulations 4 hours, be cooled to then below 60 ℃ and come out of the stove;

(4) the multiple pressure: select suitable mold to carry out multiple pressure, pressed density is 〉=8.40g/cm ³

(5) resintering: handle in the isostatic sintering stove through multiple workpiece of pressing, 930 ℃ of sintering temperatures, pressure 6～9Mp, protective atmosphere are nitrogen, argon gas, temperature retention time 2～3 hours makes described copper/rare earth oxide/carbon contact.

3, powder metallurgy extrusion production of copper/rare earth oxide/carbon contact:

(1) mixes powder: with Dy ₂O ₃Or Sm ₂O ₃After in ultrasonic equipment, disperseing with alcohol with C, add in the load weighted 200 order electrolytic copper powders, stir while adding, carry out just mixing, mixing 2 hours in mixed powder machine is then poured out and is carried out wet-milling and cross 100 mesh sieves, add copper alloy powder then, mixed in mixed powder machine 2 hours, and poured out in baking oven after 60～80 ℃ of oven dry, it is standby to cross 80 mesh sieves;

(2) system ingot:

A. with isostatic cool pressing system ingot: powder is contained in the rubber package set equably, and suppress in cold isostatic press the sealing back, and pressing pressure is 300MPa, for the later demoulding, is coated with the last layer fine graphite powders at the jacket inwall before the dress powder; Perhaps:

B. on the hydraulic press with punching block system ingot: powder is loaded on equably on the inherent hydraulic press of punching block and suppresses, pressing pressure is 3T/cm ², pressed density is 7.15～7.25g/cm ³

(3) just burn: mixing is loaded on and puts into vacuum-protective atmosphere sintering furnace in the sintering boat and carry out sintering as filler with aluminium oxide powder with workpiece; Carrying out shove charge below 80 ℃, vacuumize vacuum degree≤5 * 10 then ^-3Pa heats up then, programming rate≤10 ℃/min, and intensification limit, limit is evacuated to 300 ℃, be incubated 30 minutes, close vacuum then, charging into Ar is pressure-fired, continue to be warming up to 700 ℃ of insulations 30 minutes, proceed to 970 ℃ of insulations 4 hours, be cooled to then below 60 ℃ and come out of the stove;

(4) the multiple pressure: on hydraulic press, carry out multiple pressure, pressed density 〉=8.40g/cm ³

(5) resintering: handle in the isostatic sintering stove through multiple workpiece of pressing, 930 ℃ of sintering temperatures, pressure 6～9Mp, protective atmosphere are nitrogen, argon gas, temperature retention time 2～3 hours;

(6) extruding: on corresponding heat extruder, push; 550 ℃ of extruded sleeve temperature, the workpiece heating-up temperature is 800～850 ℃ during extruding, extrusion ratio 〉=14, extruding can be sheet material or silk material;

(7) rolling or wire drawing: draw the silk material to the thickness that requires or on wire drawing machine to corresponding diameter at cold rolling sheet material on the milling train;

(8) blanking or system rivet: make corresponding described copper/rare earth oxide/carbon contact contact or on rivet driver, make corresponding rivet with the stamping die blanking, make described copper/rare earth oxide/carbon contact.

The present invention is by adding high-melting-point, rare earth oxide Dysprosium trioxide or samarium sesquioxide and carbon that decomposition temperature is high in the copper alloy body, thereby improved its serviceability.By in copper alloy, adding Dy ₂O ₃Or Sm ₂O ₃And C, because of Dy ₂O ₃Or Sm ₂O ₃Do not react under sintering temperature with C, so the Dy that has disperse to distribute in the contact material ₂O ₃Or Sm ₂O ₃And C.This material is when electrical arc erosion, because Dy ₂O ₃Or Sm ₂O ₃Density and the density (8.0g/cm of molten copper ³) roughly suitable, so can increase its viscosity, being difficult for being pulled out, thereby making contact use smooth surface by electromagnetic force, scaling loss is little, because Dy ₂O ₃Or Sm ₂O ₃High and improved the resistance fusion welding of contact with the fusing point of C.C generates CO and CO with airborne oxygen reaction under the effect of electric arc in addition ₂Thereby, improve its oxidation resistance, so contact resistance is stable.Contact material once was used for verifying on DZ20-100 circuit breaker and the CJT1-100 A.C. contactor, and was respond well.

Four, embodiment

Below in conjunction with embodiment the present invention is remake description.

Embodiment one:

A kind of copper/rare earth oxide/carbon contact, the composition proportion of its material are (percentage by weight): carbon 2.0, Dysprosium trioxide 15, tin 1.0, cadmium 1.0, copper surplus.

Its production stage is as follows:

(1) preparation of electroplate liquid: preparing 10 liters of electroplate liquid-cyanide copper plating solution need prepare under ventilation condition.Take by weighing 1400 gram potassium cyanide during preparation and be dissolved in the warm water, take by weighing 1000 gram cuprous cyanides and slowly add in the potassium cyanide solution under constantly stirring, control adds temperature, and solution temperature can be elevated to more than 60 ℃.Taking by weighing 40g potassium hydroxide is dissolved in the distilled water.After the both is dissolved well, miscible mutually.

And can use after adding water to the stirring of regulation liquid level, filtration, analysis, adjustment.

(2) electroplate:, clean up then the sulfuric acid passivation of the corrosion resistant plate of 0.5～1.0mm; Adding granularity in electroplate liquid is the Dy of 2～4 μ m ₂O ₃With granularity be the C of 0.1～1.5 μ m, use tin cadmium copper alloy plate as anode then, corrosion resistant plate is as negative electrode, cathode-current density is 5～10A/dm ²Electroplate; The electroplating power supply DC power supply or the pulse power, the most handy pulse power, negative electrode is used the plastics mold and is shielded, and solution need stir during plating; Plating bath should be monitored the content of the suspended matter in the plating bath through outside the general plating solution maintenance during plating, regularly replenishes; Electroplating velocity is 100～200 μ m/h, coating is thick 〉=and 0.5mm.

Dy is checked in the plating back ₂O ₃Content with C; Metallographic examination requires distribution of particles even, and the gathering greater than 10 μ m can not be arranged.

(3) high-temperature process: electroplate sheet material never become rusty take off on the steel plate after, in the protective atmosphere sintering furnace, handle, 930 ℃ of sintering temperatures, protective atmosphere is nitrogen, argon gas, temperature retention time 2～hour.Thereby improve its intensity.

(4) rolling: as will to carry out cold rolling through the plating sheet material of high-temperature process to required thickness.

(5) blanking: will make corresponding workpiece through the punch press blanking through rolling plating sheet material.Residue rim charge after the punching out utilizes as anode again, thereby has improved the utilization rate of material, has reduced the cost recovery of material.

(6) high temperature is handled again: make corresponding workpiece through the punch press blanking and handle in the isostatic sintering stove; 930 ℃ of sintering temperatures, pressure 6～9MPa, protective atmosphere are nitrogen, argon gas; temperature retention time 2～3 hours makes described copper/rare earth oxide/carbon contact.

Embodiment two:

A kind of copper/rare earth oxide/carbon contact, the composition proportion of its material are (percentage by weight): carbon 0.1, Dysprosium trioxide 0.1, zirconium 0.02, cadmium 0.02, aluminium 0.01, tin 0.02, lanthanum 0.02, copper surplus.

Its production stage is as follows:

(1) mixes powder: with Dy ₂O ₃After in ultrasonic equipment, disperseing with alcohol with C, add in the load weighted 200 order electrolytic copper powders, stir while adding, carry out just mixing, mixing 2 hours in mixed powder machine is then poured out and is carried out wet-milling and cross 100 mesh sieves, add zirconium cadmium aluminium tin lanthanum copper alloy powder then, mixed in mixed powder machine 2 hours, and poured out in baking oven after 60～80 ℃ of oven dry, it is standby to cross 80 mesh sieves;

(2) compacting: select suitable mold to be pressed into corresponding workpiece, pressed density is 7.15～7.25g/cm ³

(3) just burn: mixing is loaded on and puts into vacuum-protective atmosphere sintering furnace in the sintering boat and carry out sintering as filler with aluminium oxide powder with workpiece; Carrying out shove charge below 80 ℃, vacuumize vacuum degree≤5 * 10 then ^-3Pa heats up then, programming rate≤10 ℃/min, and intensification limit, limit is evacuated to 300 ℃, be incubated 30 minutes, close vacuum then, charging into Ar is pressure-fired, continue to be warming up to 700 ℃ of insulations 30 minutes, proceed to 970 ℃ of insulations 4 hours, be cooled to then below 60 ℃ and come out of the stove;

(4) the multiple pressure: select suitable mold to carry out multiple pressure, pressed density is 〉=8.40g/cm ³

(5) resintering: handle in the isostatic sintering stove through multiple workpiece of pressing, 930 ℃ of sintering temperatures, pressure 6～9Mp, protective atmosphere are nitrogen, argon gas, temperature retention time 2～3 hours makes described copper/rare earth oxide/carbon contact.

Embodiment three:

A kind of copper/rare earth oxide/carbon contact, the composition proportion of its material are (percentage by weight): carbon 1.0, samarium sesquioxide 8.0, zirconium 0.05, cadmium 0.2, aluminium 0.05, tin 0.05, lanthanum 0.05, copper surplus.

Its production stage is as follows:

(1) mixes powder: with Sm ₂O ₃After in ultrasonic equipment, disperseing with alcohol with C, add in the load weighted 200 order electrolytic copper powders, stir while adding, carry out just mixing, mixing 2 hours in mixed powder machine is then poured out and is carried out wet-milling and cross 100 mesh sieves, add zirconium cadmium aluminium tin lanthanum copper alloy powder then, mixed in mixed powder machine 2 hours, and poured out in baking oven after 60～80 ℃ of oven dry, it is standby to cross 80 mesh sieves;

(2) system ingot:

A. with isostatic cool pressing system ingot: powder is contained in the rubber package set equably, and suppress in cold isostatic press the sealing back, and pressing pressure is 300MPa, for the later demoulding, is coated with the last layer fine graphite powders at the jacket inwall before the dress powder; Perhaps:

B. on the hydraulic press with punching block system ingot: powder is loaded on equably on the inherent hydraulic press of punching block and suppresses, pressing pressure is 3T/cm ², pressed density is 7.15～7.25g/cm ³

(3) just burn: mixing is loaded on and puts into vacuum-protective atmosphere sintering furnace in the sintering boat and carry out sintering as filler with aluminium oxide powder with workpiece; Carrying out shove charge below 80 ℃, vacuumize vacuum degree≤5 * 10 then ^-3Pa heats up then, programming rate≤10 ℃/min, and intensification limit, limit is evacuated to 300 ℃, be incubated 30 minutes, close vacuum then, charging into Ar is pressure-fired, continue to be warming up to 700 ℃ of insulations 30 minutes, proceed to 970 ℃ of insulations 4 hours, be cooled to then below 60 ℃ and come out of the stove;

(4) the multiple pressure: on hydraulic press, carry out multiple pressure, pressed density 〉=8.40g/cm ³

(5) resintering: handle in the isostatic sintering stove through multiple workpiece of pressing, 930 ℃ of sintering temperatures, pressure 6～9Mp, protective atmosphere are nitrogen, argon gas, temperature retention time 2～3 hours;

(6) extruding: on corresponding heat extruder, push; 550 ℃ of extruded sleeve temperature, the workpiece heating-up temperature is 800～850 ℃ during extruding, extrusion ratio 〉=14, extruding can be sheet material or silk material;

(7) rolling or wire drawing: cold rolling sheet material draws the silk material to corresponding diameter to the thickness that requires or on wire drawing machine on the bundle machine;

(8) blanking or system rivet: make corresponding contact or on rivet driver, make corresponding rivet with the stamping die blanking.

Claims (5)

1, a kind of copper/rare earth oxide/carbon contact, it is characterized in that: the composition proportion of its material is weight percentage: carbon 0.1～2.0, Dysprosium trioxide or samarium sesquioxide 0.1～15, any metal of zirconium, aluminium, cadmium, tin and lanthanum or any two or any two above metal mixture 0.05～2.0, copper surplus.

2, a kind of copper/rare earth oxide according to claim 1/carbon contact is characterized in that: described carbon is diamond or graphite.

3, the production method of copper/rare earth oxide/carbon contact according to claim 1 is characterized in that:

(1) preparation of electroplate liquid: take by weighing aequum potassium cyanide and be dissolved in the warm water, take by weighing the aequum cuprous cyanide and slowly add in the potassium cyanide solution under constantly stirring, control adds temperature, makes solution temperature can not be elevated to more than 60 ℃; Taking by weighing aequum potassium hydroxide is dissolved in the distilled water; After the both is dissolved well, miscible mutually, and add water to the regulation liquid level, after stirring, filter, analyze, adjusting, can use;

(2) electroplate:, clean up then the sulfuric acid passivation of the corrosion resistant plate of 0.5～1.0mm; Adding granularity in electroplate liquid is the Dy of 2～4 μ m ₂O ₃Or Sm ₂O ₃With granularity be the C of 0.1～1.5 μ m, use copper alloy plate as anode then, corrosion resistant plate is as negative electrode, cathode-current density is 5～10A/dm ²Electroplate; Electroplating power supply is used the plastics mold and is shielded with the DC power supply or the pulse power, negative electrode, and solution need stir during plating; Plating bath should be monitored the content of the suspended matter in the plating bath through outside the general plating solution maintenance during plating, regularly replenishes; Electroplating velocity is 100～200 μ m/h, coating is thick 〉=and 0.5mm;

(3) high-temperature process: electroplate sheet material never become rusty take off on the steel plate after, in the protective atmosphere sintering furnace, handle, 930 ℃ of sintering temperatures, protective atmosphere is nitrogen, argon gas, temperature retention time 2～3 hours;

(4) rolling: as will to carry out cold rolling through the plating sheet material of high-temperature process to required thickness;

(5) blanking: will make corresponding workpiece through the punch press blanking through rolling plating sheet material;

(6) high temperature is handled again: make corresponding workpiece through the punch press blanking and handle in the isostatic sintering stove; 930 ℃ of sintering temperatures, pressure 6～9MPa, protective atmosphere are nitrogen, argon gas; temperature retention time 2～3 hours makes described copper/rare earth oxide/carbon contact.

4, the production method of copper/rare earth oxide/carbon contact according to claim 1 is characterized in that:

(1) mixes powder: with Dy ₂O ₃Or Sm ₂O ₃After in ultrasonic equipment, disperseing with alcohol with C, add in the load weighted 200 order electrolytic copper powders, stir while adding, carry out just mixing, mixing 2 hours in mixed powder machine is then poured out and is carried out wet-milling and cross 100 mesh sieves, add copper alloy powder then, mixed in mixed powder machine 2 hours, and poured out in baking oven after 60～80 ℃ of oven dry, it is standby to cross 80 mesh sieves;

(2) compacting: select suitable mold to be pressed into corresponding workpiece, pressed density is 7.15～7.25g/cm ³

(3) just burn: mixing is loaded on and puts into vacuum-protective atmosphere sintering furnace in the sintering boat and carry out sintering as filler with aluminium oxide powder with workpiece; Carrying out shove charge below 80 ℃, vacuumize vacuum degree≤5 * 10 then ^-3Pa heats up then, programming rate≤10 ℃/min, and intensification limit, limit is evacuated to 300 ℃, be incubated 30 minutes, close vacuum then, charging into Ar is pressure-fired, continue to be warming up to 700 ℃ of insulations 30 minutes, proceed to 970 ℃ of insulations 4 hours, be cooled to then below 60 ℃ and come out of the stove;

(4) the multiple pressure: select suitable mold to carry out multiple pressure, pressed density is 〉=8.40g/cm ³

(5) resintering: handle in the isostatic sintering stove through multiple workpiece of pressing, 930 ℃ of sintering temperatures, pressure 6～9MPa, protective atmosphere are nitrogen, argon gas, temperature retention time 2～3 hours makes described copper/rare earth oxide/carbon contact.

5, the production method of copper/rare earth oxide/carbon contact according to claim 1 is characterized in that:

(1) mixes powder: with Dy ₂O ₃Or Sm ₂O ₃After in ultrasonic equipment, disperseing with alcohol with C, add in the load weighted 200 order electrolytic copper powders, stir while adding, carry out just mixing, mixing 2 hours in mixed powder machine is then poured out and is carried out wet-milling and cross 100 mesh sieves, add copper alloy powder then, mixed in mixed powder machine 2 hours, and poured out in baking oven after 60～80 ℃ of oven dry, it is standby to cross 80 mesh sieves;

(2) system ingot:

A. with isostatic cool pressing system ingot: powder is contained in the rubber package set equably, and suppress in cold isostatic press the sealing back, and pressing pressure is 300MPa, for the later demoulding, is coated with the last layer fine graphite powders at the jacket inwall before the dress powder; Perhaps:

B. on the hydraulic press with punching block system ingot: powder is loaded on equably on the inherent hydraulic press of punching block and suppresses, pressing pressure is 3T/cm ², pressed density is 7.15～7.25g/cm ³

(3) just burn: mixing is loaded on and puts into vacuum-protective atmosphere sintering furnace in the sintering boat and carry out sintering as filler with aluminium oxide powder with workpiece; Carrying out shove charge below 80 ℃, vacuumize vacuum degree≤5 * 10 then ^-3Pa heats up then, programming rate≤10 ℃/min, and intensification limit, limit is evacuated to 300 ℃, be incubated 30 minutes, close vacuum then, charging into Ar is pressure-fired, continue to be warming up to 700 ℃ of insulations 30 minutes, proceed to 970 ℃ of insulations 4 hours, be cooled to then below 60 ℃ and come out of the stove;

(4) the multiple pressure: on hydraulic press, carry out multiple pressure, pressed density 〉=8.40g/cm ³

(5) resintering: handle in the isostatic sintering stove through multiple workpiece of pressing, 930 ℃ of sintering temperatures, pressure 6～9MPa, protective atmosphere are nitrogen, argon gas, temperature retention time 2～3 hours;

(6) extruding: on corresponding heat extruder, push; 550 ℃ of extruded sleeve temperature, the workpiece heating-up temperature is 800～850 ℃ during extruding, extrusion ratio 〉=14, extruding can be sheet material or silk material;

(7) rolling or wire drawing: draw the silk material to the thickness that requires or on wire drawing machine to corresponding diameter at cold rolling sheet material on the milling train;

(8) blanking or system rivet: make corresponding described copper/rare earth oxide/carbon contact contact or on rivet driver, make corresponding rivet with the stamping die blanking, make described copper/rare earth oxide/carbon contact.