CN113502408B - High-conductivity copper alloy containing tellurium and nickel and preparation method thereof - Google Patents
High-conductivity copper alloy containing tellurium and nickel and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/02—Pressure casting making use of mechanical pressure devices, e.g. cast-forging
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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Abstract
The invention discloses a high-conductivity copper alloy containing tellurium and nickel and a preparation method thereof. The nickel and iron elements, the nickel-iron solid solution enlarges the plasticity of iron in the alloy, simultaneously improves the strength of pure copper, overcomes the defects of high strength and low plasticity of the copper-iron alloy in the traditional process, improves the cutting processing performance of the alloy and the high conductivity of the pure copper by the tellurium element, and obtains the high-performance copper alloy which can maintain the mechanical performance of the copper alloy and has the coexistence of high conductivity, high strength and good cutting performance.
Description
Technical Field
The invention relates to the field of new materials, in particular to a tellurium-nickel-containing high-conductivity copper alloy and a preparation method thereof.
Background
With the progress of high and new technology industry, a high-performance and high-purity new material is the key point for the development of high and new fields. The copper alloy is formed by adding one or more elements into pure copper serving as a matrix, and has excellent electrical conductivity, thermal conductivity, ductility and heat resistance, and is an indispensable material for the development of China. At present, the market generally adds at least one element of lead, tin, magnesium, nickel, zinc and the like into copper, wherein lead can improve the cutting performance of the copper alloy, but has great harm to human bodies and does not accord with the development trend of modern industry. In addition, because of the particularity of the copper alloy and the poor conductivity of high strength, the yield of the high-performance copper alloy in the production process is low, and the industrial requirement cannot be met; the quality level of the copper alloy is different, and some high-tech enterprises still depend on high-performance copper alloy imported from abroad. Therefore, the development of a high-performance copper alloy which can maintain the mechanical properties of the copper alloy and has the coexistence of no lead, high conductivity, high strength and good machinability has great significance in promoting the progress of China.
Disclosure of Invention
Aiming at the problems, the invention provides the tellurium-nickel-containing high-conductivity copper alloy, nickel and iron elements are added into copper, ferronickel is subjected to solid solution to enlarge the plasticity of iron in the alloy, and meanwhile, the strength of pure copper is improved, so that the defect that the copper-iron alloy in the traditional process is high in strength but low in plasticity is overcome; the addition of tellurium improves the machinability of the alloy and the high conductivity of pure copper.
The invention also provides a preparation method of the tellurium-nickel-containing high-conductivity copper alloy, which has the advantages of simple production process and excellent mechanical property of the prepared high-conductivity copper alloy.
The technical scheme of the invention is as follows:
a high-conductivity copper alloy containing tellurium and nickel comprises the following components in percentage by weight: 97% -98.9% of copper; 0.3% -0.7% of tellurium; 0.5 to 2 percent of nickel; 0.2 to 1 percent of iron; the balance being unavoidable impurities.
The working principle of the technical scheme is as follows:
the copper alloy is formed by adding one or more elements into pure copper serving as a matrix, and the performance of the alloy containing different added elements is different. The invention adds nickel-iron-tellurium into the pure copper as a matrix to form a quaternary alloy, wherein nickel can be infinitely and fixedly dissolved in iron, so that the tensile strength of iron elements in the copper alloy is improved, the copper alloy exerts good plasticity, and meanwhile, the nickel-iron can refine grains in the alloy by utilizing the inherent metal characteristics of the nickel-iron, so that a stable K phase is formed, and the copper alloy has better mechanical properties. The addition of tellurium element has excellent easy-cutting performance and keeps the excellent electric conduction and heat conduction performance of pure copper, and can achieve the high-performance copper alloy which can not only maintain the mechanical performance of the copper alloy, but also has the coexistence of lead-free, high electric conduction, high strength and good cutting performance.
In a further technical scheme, the inevitable impurities account for 0.01 to 0.1 percent by weight. .
In the process of preparing the copper alloy, because the temperature rise is accompanied with the phenomena of oxidation and air suction, H exists in furnace gas2、O2、N2、H20、CO、CO2、SO2And the method can not completely remove the impurities, the inventor reduces the generation of a large amount of inevitable impurities by controlling various process parameters, and in addition, the method has less side reaction due to the selection of metal elements and ensures that the prepared copper alloy liquid has high purity.
In a further technical scheme, the composition comprises the following components in percentage by weight: 98.9 percent of copper; 0.3 percent of tellurium; 0.5 percent of nickel; 0.2 percent of iron; 0.1% of unavoidable impurities.
Through the proportion of the elements, only a small amount of metal elements are added, the electric conduction, the heat conduction, the corrosion resistance and the easy processing performance of pure copper are kept, and the high-performance copper alloy has the coexistence of no lead, high electric conduction, high strength and good cutting performance.
In a further technical scheme, the composition comprises the following components in percentage by weight: 97% of copper; 0.7% of tellurium; 2% of nickel; 0.29 percent of iron; 0.01% of unavoidable impurities.
By the proportion of the elements, the pure copper is used as a matrix, the nickel and iron elements are added to improve the strength of the pure copper, the defect that the copper-iron alloy in the traditional process is high in strength and low in plasticity is overcome, and the cutting processability of the alloy and the high conductivity of the pure copper are improved by adding the tellurium element.
The invention also provides a preparation method of the tellurium-nickel-containing high-conductivity copper alloy, which comprises the following steps:
s1, weighing the components according to the weight percentage according to the composition of the raw materials for later use;
s2, preheating a smelting furnace, adding the weighed pure copper into the smelting furnace, covering graphite flakes, and heating and melting to a liquid state;
s3, after the pure copper is completely melted, adding metal nickel into the copper liquid, and continuously and slowly stirring;
s4, after the metal nickel is completely melted, sequentially adding a phosphorus-copper alloy and high-purity iron, and continuously and slowly stirring, wherein phosphorus in the phosphorus-copper alloy accounts for 0.1-0.4% of the weight of the copper liquid;
s5, slowly heating to completely melt the high-purity iron, adding pure hoofs, and continuously and slowly stirring to obtain a copper alloy liquid after the pure hoofs are completely melted;
and S6, keeping the copper alloy liquid at a constant temperature, standing, casting, forming, cooling, and taking out the casting to obtain the high-conductivity copper alloy product.
The working principle of the technical scheme is as follows:
according to the component ingredients of the copper alloy with high conductivity, the smelting furnace is preheated to prevent oxygen absorption and oxidation in the alloy smelting process, the materials are added according to the physical properties of various elements and the sequence of copper, nickel, phosphorus copper alloy, iron and hoof, and new raw materials are added after the former component is completely molten, so that the phenomena that the melting points of different elements are different, the temperature is too high or too low and impurities are increased can be prevented. The invention adopts graphite flakes as covering agent to prevent copper, nickel, iron and hoof in copper alloy from being oxidized, evaporated and aspirated. The copper and oxygen generate cuprous oxide at high temperature, the cuprous oxide is dissolved in the copper liquid to reduce the performance, the cuprous oxide is reduced into copper by the phosphorus-copper alloy, and the performance of the copper alloy is not influenced. The high-conductivity copper alloy prepared by the method has good comprehensive physical properties and mechanical properties, can be produced in a large scale, has qualified quality, and can be applied to the fields of aerospace, intelligent manufacturing, electronic information, electric power engineering and the like.
In a further technical scheme, the preheating temperature of the smelting furnace in the step S2 is 500-600 ℃, the temperature for heating and melting pure copper to liquid state is 1000-1100 ℃, the temperature for heating and melting the pure iron in the step S5 is 1100 ℃, the temperature for keeping the copper alloy liquid at the temperature of 1200 ℃ for heat preservation and standing in the step S6 is used for casting.
The temperature in the smelting process determines the quality of finished products, the defects of coarse grains, cracks, segregation and the like are easily generated by gas absorption and oxidation when the temperature is too high, the solution is not completely melted and is difficult to cast when the temperature is too low, and the prepared defective products are difficult to meet the requirements of industrial copper. Therefore, the smelting temperature and the tapping temperature (casting temperature) are selected, the fluidity of the metal is kept, the casting is easy, the purity of the product is high, and a high-quality casting can be obtained.
In a further technical scheme, the time for continuing the slow stirring in the steps S3 and S4 is 2min, and the time for continuing the slow stirring in the step S5 is 30S.
Materials are added in sequence in the alloy smelting process, the melting is discontinuous, the materials need to be stirred uniformly, the product quality is improved, the energy consumption is reduced, the production efficiency is improved, and the method is suitable for smelting new materials, intermediate products and scrap returns.
In a further technical scheme, the adding amount of the graphite flakes is 1-1.5% of the weight of the pure copper.
The graphite flake with the weight percentage of 1-1.5 percent can effectively adsorb gas, water vapor and the like in the melting furnace and reduce the porosity.
In a further technical scheme, after the high-purity iron is added in the step S4, a scrap returning material or an intermediate alloy is also added, wherein the scrap returning material is a waste casting and a casting head generated after casting, and the intermediate alloy is a binary alloy generated in the production process.
The intermediate alloy and the scrap returning material generated in the casting process are reused, so that the cost can be saved, and the product yield is high.
In a further technical solution, the casting and molding in step S6 specifically includes: and preheating the die, filling the copper alloy liquid into a die cavity, and performing hot extrusion molding.
The high-conductivity copper alloy prepared by the method has high heat fluidity and easy hot processing, and can provide required product specifications and varieties for various large-scale enterprises.
The invention has the beneficial effects that:
1. according to the high-conductivity copper alloy provided by the invention, nickel and iron elements are added into copper, ferronickel is dissolved in a solid solution to expand the plasticity of iron in the alloy, meanwhile, the strength of pure copper is improved, the defect that the strength of the added iron in the copper alloy is high but the plasticity is low in the traditional process is overcome, and the cutting processability of the alloy and the high conductivity of the pure copper are improved by adding tellurium element;
2. according to the invention, the four-element alloy is formed by adding nickel-iron-tellurium into pure copper as a matrix, so that the raw material stability is high, the side reaction is less, the four-element alloy is not easy to generate oxide slag with cuprous oxide, the purity of the fused copper alloy liquid is high, the mechanical property and the mechanical property of the copper alloy can be maintained, and the four-element alloy has the advantages of lead-free property, high conductivity, high strength and good cutting property;
3. according to the preparation method for preparing the high-conductivity copper alloy, the materials are added according to the physical properties of various elements and the sequence of copper, nickel, phosphorus-copper alloy, iron and hoof, and the addition of new raw materials after the melting of the former component is finished is strictly controlled, so that the generation of impurities caused by overhigh/overlow temperature due to different melting points of different elements can be prevented.
4. The preparation method for preparing the high-conductivity copper alloy adopts the graphite flakes as the covering agent and the phosphorus-copper alloy as the deoxidizer, synergistically reduces the by-product of copper, does not generate new harmful components, has no influence on the performance of the copper alloy, and can meet the requirement of copper on yield and quantity;
5. the copper alloy prepared by the invention integrates good physical properties and mechanical properties, can be produced in a large scale, has high quality, and can be applied to high and new fields of aerospace, intelligent manufacturing, electronic information, electric power engineering and the like.
6. The invention reasonably utilizes the returned material and the intermediate alloy, not only does not influence the quality of finished products, but also can save cost, has high product yield, and the prepared high-conductivity copper alloy has high heat fluidity and easy heat processing, and can provide required product specifications and varieties for various large-scale enterprises. Has good economic and social effects.
Detailed Description
The following examples further illustrate the invention.
Example 1:
a preparation method of a high-conductivity copper alloy containing tellurium and nickel comprises the following steps:
s1, weighing the components according to the weight percentage according to the composition of the raw materials for later use;
s2, preheating a smelting furnace, adding the weighed pure copper into the smelting furnace, covering graphite flakes, and heating and melting to a liquid state;
s3, after the pure copper is completely melted, adding metallic nickel into the copper liquid, and continuously and slowly stirring;
s4, after the metal nickel is completely melted, sequentially adding phosphorus-copper alloy and high-purity iron, and continuously and slowly stirring, wherein phosphorus in the phosphorus-copper alloy accounts for 0.4% of the weight of the copper liquid;
s5, slowly heating to completely melt the high-purity iron, adding the pure hoof, continuously and slowly stirring, and completely melting the pure hoof to obtain a copper alloy liquid;
and S6, keeping the copper alloy liquid at a constant temperature, standing, casting, forming, cooling, and taking out the casting to obtain the high-conductivity copper alloy product.
The working principle of the technical scheme is as follows:
the copper alloy is formed by adding one or more elements into pure copper serving as a matrix, and the performance of the alloy containing different added elements is different. The invention adds nickel-iron-tellurium into pure copper as a substrate to form a quaternary alloy, preheats a smelting furnace to prevent oxygen absorption and oxidation in the alloy smelting process according to the batching of each component, and feeds materials according to the physical properties of various elements and the sequence of copper, nickel, phosphorus-copper alloy, iron and hoof, wherein the nickel-iron ensures that the copper alloy has better mechanical property, and the tellurium element has excellent easy-cutting property and keeps the excellent electric conduction and heat conduction properties of the pure copper. The addition of new raw materials after the former component is melted is strictly controlled, so that the phenomenon that the melting points of different elements are different, and the generation of impurities is increased due to overhigh/overlow temperature can be prevented. The invention adopts graphite flakes as covering agent to prevent copper, nickel, iron and hoof in copper alloy from being oxidized, evaporated and aspirated. The copper and oxygen generate cuprous oxide at high temperature, the cuprous oxide is dissolved in the copper liquid to reduce the performance, the cuprous oxide is reduced into copper by the phosphorus-copper alloy, and the performance of the copper alloy is not influenced.
In another embodiment, the content of each component is in weight percent: 98.9 percent of copper; 0.3 percent of tellurium; 0.5 percent of nickel; 0.2 percent of iron.
In another embodiment, the preheating temperature of the melting furnace in the step S2 is 600 ℃, the temperature for raising the temperature to melt the pure copper into the liquid state is 1100 ℃, the temperature for raising the temperature to completely melt the high purity iron is 1100 ℃ in the step S5, and the temperature for keeping the copper alloy liquid at the temperature of 1200 ℃ and standing is kept in the step S6 for casting.
In another embodiment, the time period for the slow stirring in steps S3 and S4 is 2min, and the time period for the slow stirring in step S5 is 30S.
It can be understood that the stirring function is to fully mix the mixed materials, and the stirring time can be selected according to actual conditions.
In another embodiment, graphite flake is added in an amount of 1.5% by weight of pure copper.
In another embodiment, the high purity iron is added in step S4, and then returned materials or intermediate alloy is added, wherein the returned materials are waste castings and casting heads generated after casting, and the intermediate alloy is binary alloy generated in the production process.
The scrap returns can be classified into recyclable and discarded leftover materials according to the purity, and further, the scrap returns adopted by the invention are returned due to use without precision, materials with poor quality in the processing process or excess materials exuded from a casting die opening, can be directly used, the quality of finished products is not influenced, and the yield is higher. The waste treatment is directly carried out on the residues falling on the ground or the deteriorated copper scraps such as dust absorption, oxidation and the like, so that the influence of the returned materials on the quality is avoided.
In another embodiment, the specific operations of the casting and molding in step S6 are: preheating the die, filling the die cavity with the copper alloy liquid, and performing hot extrusion molding.
The casting molding process is the prior art, and the selected die is common flat die extrusion or common extrusion in the market. By adopting the hot extrusion process, the production cost can meet various performance requirements of the product without annealing. Of course, the feedstock of the present application is suitable for forward extrusion in a cold and hot working process and is not limited to hot production. For the casting with huge production scale, a continuous extrusion process can be adopted, and the copper alloy liquid is continuously pulled into an extrusion cavity of extrusion equipment, so that the molding is completed. The metal has strong fluidity and weak selectivity to extrusion equipment, and the prepared copper alloy has comprehensive good physical properties and mechanical properties, can be produced in a large scale, has high quality, and can be applied to high and new fields of aerospace, intelligent manufacturing, electronic information, electric power engineering and the like.
Example 2:
a preparation method of a high-conductivity copper alloy containing tellurium and nickel comprises the following steps:
respectively weighing 97% of copper, 0.7% of tellurium, 2% of nickel and 0.29% of iron by weight, and placing for later use; preheating a smelting furnace to 500 ℃, adding weighed pure copper into the smelting furnace, adding graphite flakes accounting for 1% of the weight of the pure copper to uniformly cover a copper layer, heating to 1100 ℃ at a heating rate of 50 ℃/min, adding weighed metal nickel into the copper liquid after the pure copper is completely melted into copper liquid, continuously and slowly stirring for 2min, stopping stirring and the like, adding phosphorus-copper alloy accounting for 0.1% of the weight of the copper liquid by simple substance phosphorus for about 30min, adding high-purity iron, and continuously and slowly stirring for 2min again; slowly heating to 1100 ℃, adding the high-purity hoof after the high-purity iron is completely melted again under the temperature state, continuously and slowly stirring for 30s, stopping stirring, and obtaining the copper alloy liquid after the high-purity hoof is completely melted, and transferring the copper alloy liquid to a holding furnace to stand at 1200 ℃ for standby. And meanwhile, preparing a casting die, preheating the die to 600 ℃ through power frequency induction, slowly injecting the copper alloy liquid into the die cavity, and forward extruding the copper alloy liquid to flow out of the die hole to obtain a finished product with good plasticity.
Example 3:
different from the embodiment 1, the content of each component in the embodiment is as follows by weight percent: 97.98% of copper; 0.5 percent of tellurium; 1% of nickel; 0.5 percent of iron; 0.02% of unavoidable impurities.
Example 4:
different from the embodiment 1, the content of each component in the embodiment is as follows by weight percent: 97.46% of copper; 0.5 percent of tellurium; 1.5 percent of nickel; 0.5 percent of iron; 0.04% of inevitable impurities.
Example 5:
different from the embodiment 1, the phosphorus added into the phosphorus-copper alloy accounts for 0.2 percent of the weight of the copper liquid, and the rest technological parameters are the same.
And (3) performance testing:
the high-conductivity copper alloy containing tellurium and nickel provided by the invention is subjected to corresponding performance tests. The commercial lead-copper-iron alloy is used as a comparative example.
Testing the strength of the alloy according to GB/T-3851-1983 method for testing the transverse exercise strength of the hard alloy; the cutting performance and the conductivity were examined by the institute of nonferrous metallurgy, Inc., of Sichuan province. The results are shown in Table 1.
Table 1 is a table of performance test results corresponding to the embodiments of the present invention:
as can be seen from Table 1, the high-conductivity copper alloy containing tellurium and nickel provided by the invention has high performance, the strength of the copper alloy is at least greater than 550Mpa, the conductivity of the copper alloy reaches more than 60% through products prepared by different raw material proportions, and the defect that the traditional alloy can not give consideration to both machinability and strength is overcome. And the strength, plasticity and conductivity of the composite material are all higher than those of the prior art, and the composite material has great significance for the progress of social economy.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which shall all fall within the protection of the present invention.
Claims (4)
1. A preparation method of high-conductivity copper alloy containing tellurium and nickel is characterized in that,
the high-conductivity copper alloy containing tellurium and nickel comprises the following components in percentage by weight: 97% of copper; 0.7% of tellurium; 2% of nickel; 0.29 percent of iron; 0.01% of unavoidable impurities;
the preparation method of the tellurium-nickel-containing high-conductivity copper alloy comprises the following steps:
s1, weighing the components according to the weight percentage according to the composition of the raw materials for later use;
s2, preheating a smelting furnace, adding the weighed pure copper into the smelting furnace, covering graphite flakes, and heating the smelting furnace to melt the pure copper into a liquid state;
s3, after the pure copper is completely melted, adding metal nickel into the copper liquid, and continuously and slowly stirring;
s4, after the metal nickel is completely melted, sequentially adding a phosphorus-copper alloy and high-purity iron, and continuously and slowly stirring, wherein phosphorus in the phosphorus-copper alloy accounts for 0.1-0.4% of the weight of the copper liquid;
s5, slowly heating to completely melt the high-purity iron, adding pure tellurium, and continuously and slowly stirring to completely melt the pure tellurium to obtain a copper alloy liquid;
s6, keeping the copper alloy liquid at a constant temperature, standing, casting, forming and cooling, and taking out a casting to obtain a high-conductivity copper alloy product;
the preheating temperature of the smelting furnace in the step S2 is 500-600 ℃, the temperature for heating and melting pure copper to liquid state is 1000-1100 ℃, the temperature for heating and melting the pure iron in the step S5 is 1100 ℃, the temperature for keeping the copper alloy liquid at the temperature of 1200 ℃ for casting is kept in the step S6;
the casting and molding in the step S6 specifically includes: and preheating the die, filling the copper alloy liquid into a die cavity, and performing hot extrusion molding.
2. The method as claimed in claim 1, wherein the slow stirring is continued for 2min in each of steps S3 and S4, and the slow stirring is continued for 30S in step S5.
3. The method for preparing the tellurium-nickel-containing high-conductivity copper alloy as claimed in claim 1, wherein the amount of the graphite flakes added is 1% -1.5% of the weight of the pure copper.
4. The method of claim 1, wherein the step S4 is performed by adding high purity iron and then adding scrap or intermediate alloy, wherein the scrap is waste casting and casting head after casting, and the intermediate alloy is binary alloy generated in the production process.
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| CN107406916A (en) * | 2015-03-30 | 2017-11-28 | 株式会社神户制钢所 | Heat dissipation element copper alloy plate and heat dissipation element |
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