CN107034381A - A kind of Cu Ni Co Sn P copper alloys and preparation method thereof - Google Patents

Abstract

The application discloses a Cu-Ni-Co-Sn-P copper alloy, comprising the following components by weight percentage: 0.2% to 1.0% of Ni, 0.5% to 1.5% of Sn, 0.2% to 1.0% of Co, 0.001% to 0.01% of P, and the rest is Cu. Its tensile strength σb can reach 550-700MPa, plastic elongation δ is 8%-15%, electrical conductivity is 35%-45% IACS, stress relaxation resistance (120°C, 1000h) ≥ 95%, and softness resistance (450°C, 3min) ≥ 150HV, heat shrinkage (450°C, 1min) ≤ 0.01%. The invention also discloses a preparation method of Cu-Ni-Co-Sn-P copper alloy.

Description

A kind of Cu-Ni-Co-Sn-P copper alloy and preparation method thereof

technical field

The invention relates to the technical field of copper alloy materials, in particular to a Cu-Ni-Co-Sn-P copper alloy and a preparation method thereof.

Background technique

With the rapid development of electronic communication and other related information industries, the demand for integrated circuits is increasing, and the requirements for them are also getting higher and higher. The core of modern electronic information technology is the integrated circuit, and the chip and the lead frame are packaged to form an integrated circuit. As the main structural material of integrated circuit packaging, lead frames play an important role in the circuit, such as carrying chips, connecting chips and external circuit board electrical signals, and mounting and fixing. Its main functions are: connecting external circuits and transmitting electrical signals; dissipating heat to the outside world to play a role in heat conduction; supporting and fixing the chip, and the overall supporting frame structure of the shell is assembled by IC to protect internal components. It can be seen that lead frames play a huge role in integrated circuit devices and various assembly procedures. How to effectively improve the thermal conductivity, electrical conductivity, strength, hardness, high softening temperature, heat resistance, oxidation resistance, corrosion resistance, weldability, and plastic packaging of lead frame materials Flexibility, repeated bending and processing performance have become more prominent problems in the development of integrated circuits.

Electronic information products continue to be miniaturized, thinned, lightweight, high-speed, multi-functional and intelligent, and integrated circuits are developing in the direction of large-scale and ultra-large-scale, which promotes the lead frame to lead pitch miniaturization and multi-pin direction of development. This requires that the various properties of the lead frame material be more excellent and comprehensive. It is mainly highlighted in the following aspects: the miniaturization of the lead frame requires that it should have higher strength and hardness; the high integration and high density of the integrated circuit makes it dissipate more heat per unit volume, which requires the lead frame material to have Excellent thermal conductivity; good electrical conductivity is a must for lead frame materials, given the detrimental effects of capacitive and inductive effects. In addition, it also needs to have the performance requirements of good softening resistance and low thermal shrinkage rate.

At present, the copper-based lead frames in the domestic market mainly include several alloys such as C19210, C19400 and C70250. Among them, the conductivity of the C19210 alloy is greater than 80% IACS, but the strength is only about 400MPa, which cannot meet the strength requirements of large-scale integrated circuits and limits its Further use; while the conductivity of C19400 alloy is greater than 60% IACS, and the tensile strength reaches 450-600 MPa, it still cannot meet the strength of VLSI and the development needs of multi-pin, and it is mainly used in low-end lead frame materials; C70250 Alloy is a high-end lead frame material for integrated circuits, its electrical conductivity is about 45% IACS, and its tensile strength is greater than 600MPa. However, in the production process of this alloy, special quenching and aging procedures and equipment are required, and the production process is relatively complicated. , the production cost is high, and the current domestic products can only meet the requirements of middle and low-end customers, which affects the industrialization and application of alloys.

As the global economy continues to slump and manufacturing and processing companies are facing severe market competition pressure, the development of low-cost and high-performance new lead frame materials can not only promote the development of lead frame materials in my country, but also enrich the copper alloy strips for lead frames in my country. The variety series of materials can promote the technological innovation and product upgrading of downstream enterprises.

Therefore, how to provide a copper alloy that is suitable for making a lead frame and has high strength, hardness, electrical conductivity, stress relaxation resistance, softness resistance, and low thermal shrinkage performance, so as to adapt to the current situation. The industrial development needs of the stage is a technical problem that those skilled in the art urgently need to solve.

Contents of the invention

The purpose of the present invention is to provide a Cu-Ni-Co-Sn-P copper alloy, which is suitable for making lead frames, and has high strength, hardness, electrical conductivity, stress relaxation resistance and softness resistance Performance, as well as low thermal shrinkage performance, can meet the needs of industrial development at this stage. Another object of the present invention is to provide a method for preparing Cu-Ni-Co-Sn-P copper alloy.

In order to solve the above-mentioned technical problems, the technical solution provided by the invention is:

A Cu-Ni-Co-Sn-P copper alloy, comprising the following components in weight percent: 0.2% to 1.0% of Ni, 0.5% to 1.5% of Sn, 0.2% to 1.0% of Co, 0.001% to 0.01% % P, the rest is Cu.

Preferably, 0.5≤(weight percentage of Ni+weight percentage of Co)≤1.5; 0.8≤(weight percentage of Ni+weight percentage of Co)/(weight percentage of Sn+weight percentage of P)≤2.

Preferably, the copper alloy further includes at least one of the elements Zr, Mn, Cr, Fe and B;

And 0.75-D/400≤(the sum of weight percentages of Zr, Mn, Cr, Fe and B added elements)≤0.75-D/500, wherein D is the thickness of the ingot, 200mm≤D≤300mm.

Preferably, it includes the following components in weight percentage: 0.5%-0.8% Ni, 0.9%-1.2% Sn, 0.3%-0.5% Co, 0.004%-0.007% P, and the rest is Cu.

The present application also provides a method for preparing the above-mentioned Cu-Ni-Co-Sn-P copper alloy, which includes successively melting and casting, hot rolling, spraying treatment, face milling, rough rolling, bell jar annealing, intermediate rolling, Secondary bell annealing, finish rolling, bright annealing, finish rolling and bell aging.

Preferably, the following steps are included:

(1) Melting and casting: adopt smelting, degassing, removing inclusions, and prepare copper alloy by electromagnetic stirring or mechanical stirring;

The melting temperature is 1200-1300°C, and the casting temperature is 1150-1250°C;

During the smelting process, the proportion of elements is precisely controlled, and the content of each element is tested online to supplement and adjust the proportion of copper alloy elements, and complete the entire casting process;

(2) Hot rolling: the hot rolling temperature is 800～950℃, and the hot rolling time is 4～8h;

(3) Spray treatment: the finishing temperature of hot rolling is kept above 700°C;

(4) Face milling: the milling amount of the upper knife is 0.4mm to 1mm, and the milling amount of the lower knife is 0.4mm to 1mm;

(5) Rough rolling: the reduction rate of rough rolling is 60% to 80%;

(6) One-time bell jar annealing: the annealing temperature is 500-550°C, and the holding time is 5-7h;

(7) Intermediate rolling: the reduction rate of intermediate rolling is 60% to 80%;

(8) Secondary bell jar annealing: the annealing temperature is 500-550°C, and the holding time is 5-7h;

(9) The bottom of the finish rolling: the reduction rate of the bottom of the finish rolling is 40% to 60%;

(10) Bright annealing: the annealing temperature is 850-900°C, and the speed is 5-10m/min;

(11) Finish rolling: the reduction rate of finish rolling is 30-40%;

(12) Bell jar aging: the aging temperature is 250-300°C, and the holding time is 4-6 hours.

The application provides a Cu-Ni-Co-Sn-P copper alloy and a preparation method thereof. The Cu-Ni-Co-Sn-P copper alloy provided by the invention is suitable for making a lead frame and has a higher Intensity, hardness, electrical conductivity, stress relaxation resistance and softness resistance, and low thermal shrinkage performance can meet the needs of industrial development at the present stage; the preparation method of the copper alloy of the present invention includes adding Electromagnetic field stirring, ultrasonic field stirring, and mechanical stirring are used to prepare ingots to improve the shape of the solid-liquid phase interface during alloy solidification and reduce the depth of melt pockets. At the same time, it effectively breaks the dendrite structure and reduces the alloy The macro and micro segregation of elements solves the problems of porosity and porosity in the process of smelting and casting, and the easy cracking of ingots in the process of pressure processing, which is not conducive to subsequent processing, and the problems of low yield. It has been verified by tests that the tensile strength σb of the Cu-Ni-Co-Sn-P copper alloy provided by this application can reach 550-700 MPa, the plastic elongation δ is 8%-15%, and the electrical conductivity is 35%-45% IACS , Stress relaxation resistance (120°C, 1000h) ≥ 95%, softness resistance (450°C, 3min) ≥ 150HV, heat shrinkage (450°C, 1min) ≤ 0.01%. It can be widely used in the production of lead frames in connector components for medium and low temperature work such as air conditioners and automobiles.

Description of drawings

Fig. 1 is the TEM structure diagram of copper alloy after bell jar aging treatment in the embodiment of the present invention;

Fig. 2 is a graph showing the stress relaxation resistance of the finished copper alloy in the embodiment of the present invention.

detailed description

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than limiting the claims of the present invention.

The present application provides a Cu-Ni-Co-Sn-P copper alloy, comprising the following components in weight percentage: 0.2% to 1.0% of Ni, 0.5% to 1.5% of Sn, 0.2% to 1.0% of Co, 0.001% to 0.01% of P, and the rest is Cu.

The role of the added alloying elements:

Ni: Nickel element can play a role of solid solution strengthening. In addition, the addition of nickel element can also increase the wettability of the alloy and improve the weldability of the lead frame material.

Sn: Due to the large difference in radius between tin atoms and copper atoms, adding a small amount of tin elements to copper alloys can cause large lattice distortions and effectively hinder the movement of dislocations, especially in the process of alloy stress relaxation. Dragging dislocations improves the stress relaxation resistance of the alloy.

Co: Cobalt element can play a role of solid solution strengthening, in addition, cobalt element can also effectively improve the softening resistance and fatigue resistance of the alloy.

P: Phosphorus combines with nickel and cobalt elements to form (Ni, Co)P phase, which can effectively hinder the movement of dislocations and improve the stress relaxation resistance of the alloy.

Ni, Co combine with Sn, P to form a second phase effective for age hardening, inhibit grain growth and increase softening temperature.

In one embodiment of the present application, 0.5≤(weight percent of Ni+weight percent of Co)≤1.5; 0.8≤(weight percent of Ni+weight percent of Co)/(weight percent of Sn+weight percent of P) ≤2.

When (weight percent of Ni + weight percent of Co)/(weight percent of Sn + weight percent of P) > 2%, too much primary phase will be formed during solidification, and it is difficult to dissolve back during solid solution treatment Into the copper matrix, thereby reducing the processing performance of the alloy; if (weight percentage of Ni + weight percentage of Co) / (weight percentage of Sn + weight percentage of P) < 0.8, the strength of the alloy is insufficient.

In one embodiment of the present application, the copper alloy further includes at least one of the elements Zr, Mn, Cr, Fe and B;

And 0.75-D/400≤(the sum of weight percentages of Zr, Mn, Cr, Fe and B added elements)≤0.75-D/500, wherein D is the thickness of the ingot, 200mm≤D≤300mm.

The present invention also includes the following alloy elements: at least one of Zr, Mn, Cr, Fe and B, the addition of these trace elements can refine the crystal grains and form fine dispersed precipitates, because there are a large number of such dispersed phases in the alloy The precipitated phase and the growth of grains are also hindered, so the softening resistance can be significantly improved. In fact, a variety of alloying elements do not work in isolation, and their effects are mutual, and the amount of any one of the components will change the properties of the alloy. Each element has its own independent effect, but after the elements are combined with each other, the elements excite and promote each other, and the synergistic effect is very obvious, so that the processability, mechanical properties, stress relaxation resistance and softening resistance of the copper alloy have been improved. Significantly increased.

The addition of trace elements should satisfy: the copper alloy also includes at least one of the elements Zr, Mn, Cr, Fe and B;

And 0.75-D/400≤(the sum of the weight percentages of Zr, Mn, Cr, Fe and B added elements)≤0.75-D/500, where D is the thickness of the ingot, 200mm≤D≤300mm;

When the alloy provided by the present invention includes all five kinds of Zr, Mn, Cr, Fe and B elements, 0.75-D/400≤(weight percentage of Zr+Mn weight percentage+Cr weight percentage+Fe weight percentage+B % by weight) ≤ 0.75-D/500, where D is the thickness of the ingot, 200mm ≤ D ≤ 300mm; to ensure that in the core of a large-sized ingot with a slow solidification cooling rate, no or less formation of Once solidified precipitated phase.

In one embodiment of the present application, the above-mentioned Cu-Ni-Co-Sn-P alloy includes the following components in weight percentage: 0.5% to 0.8% of Ni, 0.9% to 1.2% of Sn, 0.3% to 0.5% Co, 0.004% ~ 0.007% of P, the rest is Cu.

The present application also provides a method for preparing the above-mentioned Cu-Ni-Co-Sn-P copper alloy, which includes successively melting and casting, hot rolling, spray treatment, face milling, rough rolling, bell jar annealing, intermediate rolling, Secondary bell annealing, finish rolling, bright annealing, finish rolling and bell aging.

The preparation method of above-mentioned Cu-Ni-Co-Sn-P copper alloy specifically comprises the following steps:

(1) Melting and casting: alloys are prepared by smelting, degassing, removing inclusions, and electromagnetic stirring or mechanical stirring;

The melting temperature is 1200-1300°C, and the casting temperature is 1150-1250°C;

During the smelting process, the proportion of elements is precisely controlled, and the content of each element is tested online to supplement and adjust the proportion of alloy elements, and complete the entire casting process;

(2) Hot rolling: the hot rolling temperature is 800～950℃, and the hot rolling time is 4～8h;

(3) Spray treatment: the finishing temperature of hot rolling is kept above 700°C;

(4) Face milling: the milling amount of the upper knife is 0.4mm to 1mm, and the milling amount of the lower knife is 0.4mm to 1mm;

(5) Rough rolling: the reduction rate of rough rolling is 60% to 80%;

(6) One-time bell jar annealing: the annealing temperature is 500-550°C, and the holding time is 5-7h;

(7) Intermediate rolling: the reduction rate of intermediate rolling is 60% to 80%;

(8) Secondary bell jar annealing: the annealing temperature is 500-550°C, and the holding time is 5-7h;

(9) The bottom of the finish rolling: the reduction rate of the bottom of the finish rolling is 40% to 60%;

(10) Bright annealing: the annealing temperature is 850-900°C, and the speed is 5-10m/min;

(11) Finish rolling: the reduction rate of finish rolling is 30-40%;

(12) Bell jar aging: the aging temperature is 250-300°C, and the holding time is 4-6 hours.

The present invention controls and optimizes the type and content of elements in the copper alloy, so that the Cu-Ni-Co-Sn-P copper alloy provided by the present invention has high processability, mechanical properties, stress relaxation resistance, and Softening performance and low thermal shrinkage performance can meet the needs of stable and continuous production of qualified lead frame materials, improve the stability and continuity of lead frame material production, improve product quality and production efficiency, and meet the market requirements Requirements for frame materials with low cost and good performance stability.

The present invention has no limitation on the processing equipment and process parameters not mentioned in the above method, and the processing equipment and process parameters well-known to those skilled in the art can be used.

In order to further understand the present invention, a Cu-Ni-Co-Sn-P copper alloy provided by the present invention and its preparation method will be described in detail below in conjunction with examples, and the protection scope of the present invention is not limited by the following examples.

Example 1

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 1 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (element Zr)→sampling analysis (temperature control at 1240±10°C)→composition adjustment→drawing (temperature control at 1215±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 710°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 60%;

(6) One-time bell jar annealing: the annealing temperature is 500°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 50%;

(10) Bright annealing: the annealing temperature is 850°C, and the speed is 5m/min;

(11) Finish rolling: the reduction rate is 35%;

(12) Bell jar aging: the aging temperature is 250°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 1 in Table 2.

Example 2

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 2 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Mn)→sampling analysis (temperature control at 1250±10°C)→composition adjustment→drawing (temperature control at 1210±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 705°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 60%;

(6) One-time bell jar annealing: the annealing temperature is 500°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 75%;

(8) Secondary bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 50%;

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 6m/min;

(11) Finish rolling: the reduction rate is 40%;

(12) Bell jar aging: the aging temperature is 270°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 2 in Table 2.

Example 3

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 3 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Cr)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1215±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 708°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 65%;

(6) One-time bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 55%;

(10) Bright annealing: the annealing temperature is 870°C, and the speed is 6m/min;

(11) Finish rolling: reduction rate is 35%;

(12) Bell jar aging: the aging temperature is 260°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 3 in Table 2.

Example 4

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 4 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (B)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1220±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 711°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 65%;

(6) One-time bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 530°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 55%;

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 5m/min;

(11) Finish rolling: reduction rate is 35%;

(12) Bell jar aging: the aging temperature is 260°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 4 in Table 2.

Example 5

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 5 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Fe)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1215±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 710°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 68%;

(6) One-time bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 540°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 50%;

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 6m/min;

(11) Finish rolling: the reduction rate is 40%;

(12) Bell jar aging: the aging temperature is 250°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 5 in Table 2.

Example 6

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 6 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Zr+Mn)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1220±10°C) ;

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 703°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 68%;

(6) One-time bell jar annealing: the annealing temperature is 530°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 75%;

(8) Secondary bell jar annealing: the annealing temperature is 540°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 55%;

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 5m/min;

(11) Finish rolling: the reduction rate is 40%;

(12) Bell jar aging: the aging temperature is 270°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 6 in Table 2.

Example 7

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 7 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Cr+B+Fe)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1210±10°C ℃);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 701°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 75%;

(6) One-time bell jar annealing: the annealing temperature is 540°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 50%;

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 5m/min;

(11) Finish rolling: the reduction rate is 40%;

(12) Bell jar aging: the aging temperature is 280°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 7 in Table 2.

Example 8

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 8 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Zr+Cr+B+Fe)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1220°C ±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 706°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 75%;

(6) One-time bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 500°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 55%;

(10) Bright annealing: the annealing temperature is 880°C, and the speed is 7m/min;

(11) Finish rolling: reduction rate is 35%;

(12) Bell jar aging: the aging temperature is 250°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 8 in Table 2.

Example 9

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 9 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Zr+Mn+Cr+Fe)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1220°C ±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 708°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 78%;

(6) One-time bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 70%;

(8) Secondary bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(9) Bottom left in finish rolling: the reduction rate is 60%.

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 5m/min

(11) Finish rolling: the reduction ratio is 40%.

(12) Bell jar aging: the aging temperature is 270°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 9 in Table 2.

Example 10

The alloy of the present invention adopts the following raw materials for smelting: electrolytic copper, pure nickel, pure tin, pure cobalt, and copper-phosphorus master alloy. The composition of the alloy is shown in Example 10 of Table 1.

(1) Melting and casting: (bright wire copper 30% + recycled copper 70%) + nickel + cobalt covering (calcined charcoal + electrode graphite powder) → melting + tin + 25% copper-phosphorus master alloy → slag removal → heating (1220°C )→degassing (10min)+75% copper-phosphorus master alloy+other trace elements (Zr+Mn+Cr+B+Fe)→sampling analysis (temperature control at 1220±10°C)→composition adjustment→drawing (temperature control at 1210±10°C);

(2) Hot rolling: the hot rolling temperature is 900°C, and the holding time is 6h;

(3) Spray treatment: the finishing temperature of hot rolling is 703°C;

(4) Face milling: upper knife 0.5mm, lower knife 0.5mm;

(5) Rough rolling: the reduction rate is 75%;

(6) One-time bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(7) Intermediate rolling: the reduction rate is 78%;

(8) Secondary bell jar annealing: the annealing temperature is 550°C, and the temperature is kept for 5 hours;

(9) The end of finishing rolling: the reduction rate is 45%;

(10) Bright annealing: the annealing temperature is 860°C, and the speed is 5m/min;

(11) Finish rolling: reduction rate is 35%;

(12) Bell jar aging: the aging temperature is 250°C, and the temperature is kept for 4 hours.

After the above processing such as casting, hot rolling, spray treatment, face milling, rough rolling, first bell annealing, intermediate rolling, second bell annealing, finish rolling with bottom, bright annealing, finish rolling, bell aging, etc., Its properties are shown in Example 10 in Table 2.

The alloy composition formula (wt%) of table 1, embodiment 1-10

The alloy performance table of table 2, embodiment 1-10

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. a kind of Cu-Ni-Co-Sn-P copper alloys, it is characterised in that include the component of following percetage by weight：0.2%~ 1.0% Ni, 0.5%~1.5% Sn, 0.2%~1.0% Co, 0.001%~0.01% P, remaining is Cu.

2. copper alloy according to claim 1, it is characterised in that 0.5≤(Ni percetage by weight+Co weight percent Number)≤1.5；0.8≤(Ni percetage by weight+Co percetage by weight)/(Sn percetage by weight+P percetage by weight) ≤2。

3. copper alloy according to claim 1, it is characterised in that the copper alloy also include element Zr, Mn, Cr, Fe with At least one of and B；

And 0.75-D/400≤(the percetage by weight sum of institute's addition element in Zr, Mn, Cr, Fe and B)≤0.75-D/ 500, wherein D are the thickness of ingot casting, 200mm≤D≤300mm.

4. copper alloy according to claim 1, it is characterised in that include the component of following percetage by weight：0.5%~ 0.8% Ni, 0.9%~1.2% Sn, 0.3%~0.5% Co, 0.004%~0.007% P, remaining is Cu.

5. the preparation method of the Cu-Ni-Co-Sn-P copper alloys described in a kind of claim 1, it is characterised in that including entering successively Capable founding, hot rolling, spray process, milling face, roughing, a bell jar annealing, in roll, the annealing of secondary bell jar, finish rolling are kept on file, light Annealing, finish rolling and bell jar timeliness.

6. preparation method according to claim 5, it is characterised in that comprise the following steps：

(1) founding：Copper alloy is prepared using melting, degasification, except being mingled with, and by electromagnetic agitation or mechanical agitation mode；

Smelting temperature is 1200~1300 DEG C, and casting temperature is 1150~1250 DEG C；

In fusion process, accurate control element proportioning, by chemically examining the content of each element, supplement adjustment copper alloying element online Between proportioning, and complete whole casting process；

(2) hot rolling：Hot-rolled temperature is 800~950 DEG C, and the hot rolling time is 4~8h；

(3) spray process：Hot rolling finishing temperature is maintained at more than 700 DEG C；

(4) milling face：The milling face milling amount of upper slitter is 0.4mm~1mm, and the milling face milling amount of lower knife is 0.4mm~1mm；

(5) roughing：The reduction ratio of roughing is 60%~80%；

(6) bell jar annealing：Annealing temperature is 500~550 DEG C, and soaking time is 5~7h；

(7) rolled in：In the reduction ratio that rolls be 60%~80%；

(8) secondary bell jar annealing：Annealing temperature is 500~550 DEG C, and soaking time is 5~7h；

(9) finish rolling is kept on file：The reduction ratio that finish rolling is kept on file is 40%~60%；

(10) bright annealing：Annealing temperature is 850~900 DEG C, and speed is 5-10m/min；

(11) finish rolling：The reduction ratio of finish rolling is 30~40%；

(12) bell jar timeliness：Aging temp is 250~300 DEG C, and soaking time is 4~6h.