CN101054654A - High-strength high-conductivity oxidation-resisting low-silver copper-base alloy and preparation thereof - Google Patents
High-strength high-conductivity oxidation-resisting low-silver copper-base alloy and preparation thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 19
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- 238000000576 coating method Methods 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
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- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
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Abstract
A copper base alloy, which possesses high-strength, high conductivity, oxidation resistance and contains silver of low content, is characterized in that said high-strength high-conductivity oxidation-resistance low-silver copper base alloy is composed of low-silver copper base alloy powder, diamond powder of 0.2-1.0% and graphitized nanometer carbon fibre and is prepared through a powder metallurgy technological process, wherein said low-silver copper base alloy powder contains Ag of 0.08 -0.12%, Y, La and Ce of 0.05 -0.5% or one of misch metal or mixture of several misch metal. Said alloy in accordance with the present invention possesses higher intensity and hardness, stronger anti-crackle forming and stomatic expandability, and exhibits definite puddle welding resistance and better electroconductive performances at the same time.
Description
Technical field
The present invention relates to copper base conductive material prescription and preparation technology.
Background technology
The outstanding feature of oxygen free copper is specific conductivity IACS＞100, is ideal electro-conductive material and instrument material.Because intensity, hardness and softening temperature are low excessively, its over-all properties can not satisfy the growing particular requirement to material of science and technology.
Equally as good conductor, that conductive copper alloy conduction working order is in sometimes is low, in and in the high temperature oxidation atmosphere, conductive copper commonly used, because oxidation makes oxide thickness and the potential drop on oxide film on the conductive pieces contact surface continue to increase, the oxide film that thickens can further improve contact resistance, the temperature rise of electric-conductor further improves, and oxidation is also just constantly accelerated, and will cause inefficacy when reaching certain threshold value.Therefore the resistance of oxidation that how to improve the conduction copper material is significant to the work-ing life that prolongs basic, normal, high temperature conductive pieces.
With oxygen free copper is matrix. by adding the new copper alloy that trace element is obtained, under specific conductivity descends very few situation, improving its hardness, intensity, softening temperature, recrystallization temperature and resistance of oxidation significantly, is one of main direction of current copper alloy research.
Summary of the invention
The object of the present invention is to provide a kind of low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting, this alloy has higher intensity, hardness, and the stronger cracking resistance line and the extendability of pore also have certain anti-melting welding ability, conductivity preferably simultaneously.
The present invention specifically provides a kind of low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting, it is characterized in that:
The low-silver copper-base alloy of described high-strength high-conductivity oxidation-resisting is prepared by the powder metallurgical technique method by the bortz powder of copper base alloy powder and 0.2～1.0% and 0.05～0.1% graphited carbon nano fiber;
Described low yellow gold powder contains 0.08～0.12% Ag, 0.05～0.5% Y, La, Ce or mishmetal a kind of or the mixing that they are several.
In the low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting of the present invention,
Described low yellow gold powder contains In, Te, Zr, Zn, Ti, Sn, Mg, Al, the Cr of 0.5-1.5%, Nb, Ta, Mo a kind of or the mixing that they are several.
Generally, add a spot of silver in the oxygen free copper and through excessive deformation process, can be very big improve its intensity, hardness; Yellow gold has good electricity, thermal conduction and erosion resistance, also have good mobility and wetting property, after the main adding small amount of silver, the low yellow gold of powder metallurgy preparation has good cold and hot working performance (extruding, wire drawing), certainly add-on acts on not quite very little, if add-on also can increase cost too much.If wherein add a spot of chromium or zirconium again, intensity and hardness also have raising by a relatively large margin.Though yellow gold does not reduce the resistance of oxidation of copper base alloy, not improve yet, particularly anti-electric arc and anti-curability are not good, and hardness and intensity are also enough not high.
Diamond has performances such as fusing point height (～3700 ℃), hardness be big, wear-resistant, adopt powder metallurgy process in the copper matrix, to add tiny metal stone granulate, can play dispersion-strengthened action, improve hardness and wear resistance, this just requires diamond particles to answer the disperse uniform distribution in material.Use as contact, good anti-melting welding effect can be arranged.But research finds that also diamond is the only element that quickens copper and alloy corrosion thereof.
Carbon nano fiber is meant the carbon fiber of diameter at 80～200nm, and is straight, bigger length-to-diameter ratio is arranged, and conductivity is good, after greying (more than 2400 ℃) processing, its resistivity can reduce by 5 times, and himself resistance is suitable with pure metallic nickel, and Young's modulus increases substantially; And the copper base alloy of powder metallurgy preparation exists crackle and pore, be this class material electrically contacted source of wear and oxidation source, formation of crack, the work-ing life of this material can be obviously accelerated in the existence of crackle and pore.The graphitization nano carbon fiber guarantees that not only conductivity does not descend, and can also strengthen matrix strength, improves the expansion effect of crackle and pore and preferential oxidation and the copper of oxidation carried out the reductive effect when surpassing 550 ℃.
If having only diamond and carbon nano fiber strengthens, the resistance of oxidation of copper base alloy can descend significantly so, the addition of diamond and carbon nano fiber is many more, the resistance of oxidation of copper base alloy is poor more, and handle by adding a spot of silver and carrying out gross distortion, can improve the intensity of copper base alloy equally, can reduce the usage quantity of diamond and wear-resisting charcoal fiber again, improve the resistance of oxidation of copper base alloy.
Improve the contradiction between antioxidant property and the maintenance high conductivity, adopt and add yttrium, cerium, lanthanum or norium alloying element as copper, discovery is when suitable add-on, specific conductivity does not only reduce on the contrary and slightly improves, and also finds to add in the copper antioxidant property that rare earth alloy such as yttrium or mixing system can very obviously be improved copper base alloy low temperature and middle temperature simultaneously.Find that simultaneously rare earth not only can improve the resistance of oxidation of copper alloy, and can improve the intensity of copper alloy and the recrystallization temperature of raising copper alloy.
Except that rare earth, also have some elements as In, Te, Zr, Zn, Ti, Sn, Mg, Al, Cr, very little after the alloying of Nb, Ta, Mo and copper to conductivity influence, but also can improve copper-based material medium and high temperature anti-oxidant, anti-ablation property and corrosion resistance nature or improve its intensity and hardness.To the Cu-Cd alloy oxidation and the performance aspect the corrosion carried out research and found, the interpolation of suitable cadmium has the improvement effect to the high temperature oxidation resistance of copper base alloy in oxidizing medium, can reduce contact temperature and have the arc extinguishing effect by its vaporization as contact material the time simultaneously.But the toxicity of cadmium is big, and the RoHS of European Union regulation can not be used.And elements such as In, Te, Zn, Sn, Mg, Al also can play the effect similar to cadmium.Other element and copper matrix alloy have been eliminated and can have been improved beyond the oxidation-resistance of alloy, can also improve the intensity and the wear resistance of alloy.General alloy element all has limited solid solubility in copper, can adopt ageing strengthening to handle, and obtains the strengthening phase constituent element that small and dispersed distributes.
Low solid solubility anti-oxidation metal constituent element such as the extremely low element of solid solubility in the copper matrix such as Cr, Mo, Nd and Ta, obviously, the adding of these elements has certain effect to antioxidant property, intensity and the anti-ablation property that improves matrix.The adding of such alloy simultaneously also can improve recrystallization temperature.
Just be based on above analysis, the present invention proposes this new low yellow gold: add 0.1% silver and implement gross distortion (extruding) to improve intensity, the hardness of alloy, conductivity is unaffected simultaneously; Add a spot of graphitization nano carbon fiber and can improve the extendability of the cracking resistance line of low yellow gold and pore and have certain reducing property, also have certain anti-melting welding ability simultaneously.Add a small amount of rare earth and can improve the resistance of oxidation of alloy greatly, also improved the conductivity and the intensity hardness number of alloy simultaneously in low temperature and middle temperature; Other looks composition In, Te, Zr, Zn, Ti, Sn, Mg, Al, Cr that the application scenario adds, the adding of Nb, Ta, Mo etc. or further improve resistance of oxidation or the arc extinguishing ability of alloy when medium and high temperature is worked, the perhaps intensity that alloying and ageing treatment can strengthening materials.Above composition and copper are made low yellow gold powder by aerosolization or water atomization technology jointly,, need reduce processing it if there is oxidation on low yellow gold powder surface.To hang down yellow gold powder and a spot of micro mist diamond and graphitization nano charcoal fiber afterwards, pass through powder metallurgical technique, the dispersion-strengthened low-silver copper-base alloy improves the intensity, hardness, abrasion resistance properties of low yellow gold, uses as contact and also have anti-preferably melting welding effect.
The present invention also provides the preparation method of the low-silver copper-base alloy of above-mentioned high-strength high-conductivity oxidation-resisting, it is characterized in that:
---with copper base alloy powder and diamond and graphitization nano carbon fiber under vacuum or protective atmosphere, the copper base mixed powder of preparing through powerful mixing or high-energy ball milling;
---above-mentioned low-silver copper-base mixed powder is directly placed graphite or metallic graphite carbon composite die, in protective atmosphere or vacuum tightness 100～1 * 10
-4Pa is at 450～600 ℃ of annealing of temperature, 0～5h; Afterwards at 470～920 degree, under vacuum condition (100～1 * 10
-4Pa) directly hot pressing densification, pressurize 0.1～3 hour is incubated 0～1 hour; At 600～960 ℃,, obtain the copper alloy block again at protective atmosphere or vacuum condition sintering 0～10h;
---above-mentioned copper alloy block is obtained needed product through cold and hot deformation technique.
Among the preparation method of the low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting of the present invention, described cold and hot deformation technique is that the copper alloy block after the described densification is heated to 450～750 ℃, push on extrusion machine, extrusion ratio is 10～50, directly pushes making sheet or is squeezed into silk.
Among the preparation method of the low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting of the present invention, need under vacuum or protective atmosphere, to carry out ageing treatment, 500～800 ℃ of treatment temps, 1～8 hour treatment time through the product after the cold and hot distortion.
Among the preparation method of the low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting of the present invention, described preferably copper facing of graphited carbon nano fiber surface.
Among the preparation method of the low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting of the present invention, in the described low-silver copper-base mixed powder, the content of copper is more preferably greater than 97%.
Among the preparation method of the low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting of the present invention, described hot pressing and sintering process can repeat 1～2 time.
Advantage of the present invention is:
Because the adding of small amount of silver makes the cold and hot working performance of disguising powder metallurgical products be greatly improved in the low yellow gold, performances such as intensity, hardness also have raising simultaneously.The adding of rare earth and other element has improved the intensity of copper alloy greatly, and the conductivity sacrifice seldom simultaneously.Making has the diamond of dispersion-strengthened action and the add-on of graphitization nano charcoal fiber to significantly reduce, and the minimizing of diamond and nano carbon fiber has improved the resistance of oxidation of copper alloy.In addition, different with common cold-rolled sintered technology, before compacting, the money base powder places graphite jig earlier, carries out vacuum outgas and handles, and does not have pore and gas after the hot pressing in the silver-base alloy.Thereby eliminated the sealed porosity of colding pressing and may form, a step annealing, hot pressing, diffusion realize the densification of Ag-based electrical contact material, can obtain density greater than 99.9% low-silver copper-base electrical contact blank, give security for producing the high quality electrical contact.And vacuum hot-pressing process has been eliminated the elastic stress of powder effectively, and the resistance of powder plastic flow reduces, and helps the rearrangement and the displacement of powder particle, and densification degree improves.In a word, because comprehensive technology such as dispersed particle-strengthened, deformation complex intensifying and ageing strengthening, can realize the low-silver copper-base alloy of high strength, high rigidity, high conductivity, resistance to oxidation and low pore and crack growth.
Embodiment:
Embodiment 1
Employing contain 0.1%Ag and 0.2RE (mishmetal) gas atomization copper alloy powder (cross 150 mesh sieves), mix in high energy ball mill with 0.5% diamond and 0.08% graphitization nano charcoal fiber (copper coating), ratio of grinding media to material is 8: 1, vacuumize logical argon shield, ball milling 3 hours; The low silver-bearing copper powder mix of preparing places graphite jig, and mould internal diameter 100mm puts into vacuum hotpressing stove, the high-temperature vacuum degree reaches 0.09Pa, is warmed up to 500 ℃ of annealing 1 hour, is warmed up to 820 ℃, be hot-pressed onto densification, pressurize 20 minutes removes pressure, feed argon gas to 350Pa, be warmed up to 880 ℃, sintering 2 hours is when being cooled to 750 ℃, put into extrusion machine, extrusion ratio is 20: 1; The oxidation situation of test extruding silk and intensity, specific conductivity;
As a comparative example, very close processing condition have prepared Cu+1.0% diamond, Cu+0.2%RE, Cu+0.2%RE+1.0% diamond, Cu+0.1%Ag+0.2%RE+0.5% diamond, Cu+0.1%Ag+0.2%RE+0.5% diamond+0.08% nano carbon fiber; Equally oxidation, intensity and specific conductivity are tested.Result such as following table:
As seen from table, adding O.2%, mishmetal copper alloy oxidation weight gain reduces significantly than adding adamantine copper alloy in fine copper and the copper.The low yellow gold of (copper+0.1%Ag+0.2%RE+0.5% diamond+0.08% nano carbon fiber) this prescription is used for the adding of small amount of silver, mishmetal, no matter be intensity, or specific conductivity still is, and resistance of oxidation all is greatly improved.Make it have practical value.
Embodiment 2
Employing contains the copper alloy powder of the Al of 0.1%Ag, 0.3%Y and 1.3%, prepare by water atomization, low yellow gold powder (crossing 150 mesh sieves), 450 ℃ of hydrogen reducings, vacuumize in the mixed powder machine of three-dimensional with 0.8% diamond and 0.08% graphitization nano charcoal fiber (copper coating), logical argon shield mixed 30 fens; The low silver-bearing copper powder mix of preparing places graphite jig, mould internal diameter 100mm puts into vacuum hotpressing stove, and the high-temperature vacuum degree can reach 0.5Pa, be warmed up to 770 ℃, be hot-pressed onto densification, pressurize 20 minutes removes pressure, feed argon gas to 350Pa, be warmed up to 850 ℃, sintering 2 hours is when being cooled to 770 ℃, repeat hot pressing, be warmed up to 850 ℃ of sintering 2 hours again, when treating that temperature drops to 730 ℃, put into extrusion machine, extrusion ratio is 15: 1, be extruded into sheet material, through 20% cold rolling after, annealing, continue cold rolled annealed up to needs thickness.
Embodiment 3
Employing contains the copper alloy powder of the Cr of 0.1%Ag, 0.5%La and 0.1%, prepare by water atomization, low yellow gold powder (crossing 150 mesh sieves), 450 ℃ of hydrogen reducings, vacuumize in the mixed powder machine of three-dimensional with 0.3% diamond and 0.1% graphitization nano charcoal fiber (copper coating), logical argon shield mixed 30 fens; The low silver-bearing copper powder mix of preparing places graphite jig, and mould internal diameter 100mm puts into vacuum hotpressing stove, the high-temperature vacuum degree can reach 0.5Pa, is warmed up to 770 ℃, is hot-pressed onto densification, pressurize 20 minutes removes pressure, feeds argon gas to 350Pa, be warmed up to 850 ℃, sintering 2 hours is when being cooled to 770 ℃, put into extrusion machine, extrusion ratio is 30: 1, is extruded into a material, through after the cold-drawn, make the continuous fibers material.
| Add in the copper | Rate of oxidation mg/cm2 | IACS％ | Tensile strength Mpa |
| Oxygen free copper | 1.7 | 102 | 240 |
| 1.0% diamond | 5.5 | 98 | 500 |
| 0.2％RE | 0.45 | 103 | 380 |
| The 0.2%RE+1.0% diamond | 2.2 | 93 | 850 |
| The 0.1%Ag+0.2%RE+0.5% diamond | 0.8 | 92 | 920 |
| 0.1%Ag+0.2%RE+0.5% diamond+0.08% nano carbon fiber | 0.8 | 92 | 1050 |
Claims (10)
1, a kind of low-silver copper-base alloy of high-strength high-conductivity oxidation-resisting is characterized in that:
The low-silver copper-base alloy of described high-strength high-conductivity oxidation-resisting is prepared by the powder metallurgical technique method by the bortz powder of low-silver copper-base alloy powder and 0.2～1.0% and 0.05～0.1% graphited carbon nano fiber;
Described low yellow gold powder contains 0.08～0.12% Ag, 0.05～0.5% Y, La, Ce or mishmetal a kind of or the mixing that they are several.
2, according to the low-silver copper-base alloy of the described high-strength high-conductivity oxidation-resisting of claim 1, it is characterized in that:
Described low yellow gold powder contains In, Te, Zr, Zn, Ti, Sn, Mg, Al, the Cr of 0.5-1.5%, Nb, Ta, Mo a kind of or the mixing that they are several.
3, the preparation method of the low-silver copper-base alloy of the described high-strength high-conductivity oxidation-resisting of a kind of claim 1 is characterized in that:
---with copper base alloy powder and diamond and graphitization nano carbon fiber under vacuum or protective atmosphere, the copper base mixed powder of preparing through powerful mixing or high-energy ball milling;
---above-mentioned low-silver copper-base mixed powder is directly placed graphite or metallic graphite carbon composite die, in protective atmosphere or vacuum tightness 100～1 * 10
-4Pa is at 450～600 ℃ of annealing of temperature, 0～5h; Afterwards at 470～920 degree, under vacuum condition 100～1 * 10
-4The direct hot pressing densification of Pa, pressurize 0.1～3 hour is incubated 0～1 hour; At 600～960 ℃,, obtain the copper alloy block again at protective atmosphere or vacuum condition sintering 0～10h;
---above-mentioned copper alloy block is obtained needed product through cold and hot deformation technique.
4, according to the preparation method of the low-silver copper-base alloy of the described high-strength high-conductivity oxidation-resisting of claim 3, it is characterized in that: described cold and hot deformation technique is that the copper alloy block after the described densification is heated to 450～750 ℃, on extrusion machine, push, extrusion ratio is 10～50, directly pushes making sheet or is squeezed into silk.
5, according to the preparation method of the low-silver copper-base alloy of claim 3 or 4 described high-strength high-conductivity oxidation-resistings; it is characterized in that: under vacuum or protective atmosphere, carry out ageing treatment through the product after the cold and hot distortion; 500～800 ℃ of treatment temps, 1～8 hour treatment time.
6, according to the preparation method of the low-silver copper-base alloy of claim 3 or 4 described high-strength high-conductivity oxidation-resistings, it is characterized in that: described graphited carbon nano fiber copper coating.
7, according to the preparation method of the low-silver copper-base alloy of the described high-strength high-conductivity oxidation-resisting of claim 5, it is characterized in that: described graphited carbon nano fiber copper coating.
8, according to the preparation method of the low-silver copper-base alloy of claim 3 or 4 described high-strength high-conductivity oxidation-resistings, it is characterized in that: in the described low-silver copper-base mixed powder, the content of copper is greater than 97%.
9, according to the preparation method of the low-silver copper-base alloy of the described high-strength high-conductivity oxidation-resisting of claim 5, it is characterized in that: in the described low-silver copper-base mixed powder, the content of copper is greater than 97%.
10, according to the preparation method of the low-silver copper-base alloy of claim 3 or 4 described high-strength high-conductivity oxidation-resistings, it is characterized in that: described hot pressing and sintering process repeat 1～2 time.
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