JP7252655B2 - Continuous Extrusion Method for High-Strength, High-Conductivity Copper Alloy, Its Application, and Mold Material - Google Patents

Description

TECHNICAL FIELD The present invention relates to the technical field of non-ferrous metal processing, and in particular to a method for continuous extrusion of high-strength, high-conductivity copper alloy, its application and mold material.

Copper alloys, a typical representative of conductor materials, find wide application in the technical field of electrical engineering. With the development of the “5G” information age, further performance demands are also being made on the main copper alloy conductors used. Taking large-scale integrated circuits as an example, with the ever-increasing degree of integration of electrical circuits and the ever-improving power density, copper alloys used in lead frames for integrated circuits only have high strength. In addition, it is required to have high electrical and thermal conductivity, which ensures the lowest possible thermal effect and rapid heat release. In addition, in order to meet the requirements of semiconductor processing, the copper alloy used in lead frames must have good dimensional accuracy, that is, it must have various characteristics such as high strength, high conductivity, and high precision. not. Taking the 4G/5G mobile phone connector as an example, the most common one is the copper alloy connector used in the charging port of the mobile phone. Not only do they need to have high electrical conductivity to reduce contact resistance and thermal effects due to high current charging as much as possible, they also need to have high strength to meet the demands of shrinking dimensions. It must also maintain a set insertion force by providing stress relaxation resistance, i.e., it must have a variety of properties such as high strength, high conductivity, and high stress relaxation resistance.

The research and development of various high-strength, high-conductivity copper alloys and the technology for producing them with high efficiency and quality are important development directions of common concern in the copper alloy technology field. At present, the design of high-strength, high-conductivity copper alloy material components is mainly based on copper-silver alloy, copper-magnesium alloy, copper-tin alloy, copper-chromium alloy, copper-zirconia alloy, copper-iron alloy, copper-beryllium alloy, copper-titanium alloy. , binary copper alloys such as copper-cadmium alloys; ternary alloys such as copper-iron-phosphorus alloys, copper-nickel-silicon alloys, copper-chromium-zirconium alloys; Concentrated on component composite alloys. There are also various methods for producing high-strength, high-conductivity copper alloys.

For example, Chinese Patent Document 1 (Application No.: 201410530014.1) discloses a copper-silver alloy and its manufacturing method. First, copper and a copper-silver master alloy (intermediate alloy) are measured and calculated with a weight ratio of 80% to 99% copper (Cu) and 20% to 1% silver (Ag), then mixed and vacuum smelting furnace The crucible is evacuated to 5 × 10 ^-1 Pa or more, and then the _temperature starts to rise. Inert gas is filled up to 5×10 ³ Pa. After that, the temperature is further increased to 1150-1250° C., and after the copper and the copper-silver master alloy are completely melted, the copper-silver alloy liquid is started to be filled with an inert gas, and the mixture is further stirred for 20-30 minutes to melt the alloy. The body is cooled to obtain a copper-silver alloy blank material.

Chinese patent document 2 (application number: 201811196401.3) discloses a copper-magnesium alloy and a method for producing the same. First, the cathode copper and metallic magnesium with a copper content≧99.99% are directly put into the frequency induction furnace, and the weight percentage of magnesium is 0.16%-0.19%. Subsequently, after adding a refining agent to the copper liquid obtained by dissolving, the surface of the copper liquid is covered with flake graphite. Finally, the above cast rod for copper-magnesium alloy stranded wire is obtained by casting by a pull-up continuous casting method.

In addition, Chinese patent document 3 (application number: 201710931646.5) discloses a copper-tin alloy and its manufacturing method. The copper-tin alloy contains metallic tin, metallic copper and other impurities, and the weight ratio of each component is metallic tin 0.195-0.435%, metallic copper 99.755-99.515%, other impurities 0 0.05%. First, cathodic copper is put into a drawing furnace as a raw material and melted, then metal tin is added to the copper solution, and the alloy components are made uniform by stirring with a graphite rod, and then the blank rod is pulled up. Subsequently, the drawn blank bar made of an alloy containing tin is carried into a continuous extruder to make an extruded bar of 20 mm, and the end of the extruded bar and the tail of the wire drawing frame extruded bar of the drawing device are flash welded. After connecting by , marking the connection point, making a cut part of the copper-tin alloy contact wire finished product with an extrusion rod at the connection point, the copper-tin alloy contact wire finished product is subsequently made by drawing.

In addition, Chinese Patent Document 4 (Application No.: 201910720284.4) discloses a copper-chromium alloy and its manufacturing method. The weight percent of chromium in the alloy is 5 wt. % to 50 wt. % copper metal and chromium metal. First, under the protection of inert gas, the prepared copper chromium material powder or block is melted by vacuum non-consumable arc melting method. The vacuum non-consumable arc melted copper chromium alloy block is then inverted and melted multiple times until the alloy sample is completely melted. Then, the completely melted copper-chromium alloy is continuously melted under the protection of inert gas, the arc is extinguished quickly after melted, and the vacuum valve is opened to use the force of negative pressure. By doing so, the melted copper-chromium alloy liquid is sucked into the mold and rapidly solidified to obtain a copper-chromium alloy ingot.

Chinese patent document 5 (application number: 201610325699.8) discloses a copper-zirconia alloy and a method for producing the same. The alloy should have a weight percentage of zirconia of 0.14-0.22%, a weight percentage of zirconia plus copper of ≧99.97%, and a weight percentage of impurities of ≦0.03%. Specifically, the alloy is produced by the following steps. First, 0.1-0.25% by weight of zirconia and 99.7-99.9% by weight of copper are combined and simultaneously cast to obtain a copper-zirconia alloy ingot. Subsequently, the feeder head of the copper-zirconia alloy ingot is cut, and the oxide scale on the outside is washed to obtain a pure ingot. The ingot is then forged to form a copper-zirconia alloy bar block. Subsequently, a solution heat treatment is performed to obtain a rod block after solid solution. Subsequently, secondary forging is performed to obtain a secondary forged bar block. Subsequently, the secondary forged bar block is subjected to aging treatment to obtain an alloy blank.

Chinese Patent Document 6 (Application No.: 201810341974.4) discloses a copper-iron alloy and a method for producing the same. The composition of the alloy is Fe 4%-20%, RE 0.001-1.0%, the rest Cu, where RE is a rare earth element. For example, RE is Ce and La, and the weight percent of Ce is 0.008-0.012 wt. % and the La weight percent is between 0.05 and 0.06 wt. %. The copper-iron alloy material is produced by electro slag remelting, using a copper-iron alloy ingot melted in a vacuum induction furnace as a consumable electrode, and using a CaF ₂ -NaF slag system as a slag. there is

Chinese patent document 7 (application number: 201380056659.2) discloses a copper-beryllium alloy and a method for producing the same. Here, the Cu--Be alloy is a Cu--Be alloy containing Co, with a Co content of 0.005% to 0.12% and a Be content of 1.60% to 1.95%. The method for producing the Cu—Be alloy includes (1) a melting and casting process, (2) a homogenization process, (3) a pre-working process, (4) a solution treatment process, (5) a cold working process, and (6) an age hardening treatment process;

In addition, Chinese patent document 8 (application number: 201811313033.6) discloses a copper-titanium alloy and its manufacturing method. The weight percent ratio of each component of the alloy is Ti: 2-2.4%, Cr: 0.1-0.3%, Ni: 0.1-0.3%, Co: 0.05- 0.01% and the rest is Cu. A method of controlling the composition of the alloy includes the processing steps of (1) melting, (2) milling, (3) hot rolling, and (4) solution aging.

In addition, Chinese patent document 9 (application number: 201811196401.3) discloses a copper-cadmium alloy and its manufacturing method. The content of cadmium in the alloy is 31%-70%, melted in a reducing atmosphere, covered with charcoal or glass fragments, preheated the furnace, put in the cadmium ingot, heated and melted, the temperature is 400 ~ When the temperature reaches 750°C, the pickled electrolytic copper is added and stirred, then the temperature is raised to 400-750°C, and the pickled electrolytic copper is added and stirred, and so on. , It is cast by pouring it into a mold after letting it rest for 5 to 10 minutes.

In addition, Chinese patent document 10 (application number: 201510733708.2) discloses a copper-iron-phosphorus alloy and its production method. The composition of the alloy is Fe 2.1% to 2.6%, P 0.015% to 0.15%, Zn 0.05% to 0.20%, Pb ≤ 0.03%, Ni 0.01% ~0.1%, Sn 0.01%-0.1% and the rest Cu. The manufacturing method includes preparing and mixing raw materials according to the proportion of each component, and including processing steps such as heating, casting, hot rolling, cold rolling, heat treatment, washing, stretch straightening, and heat treatment.

In addition, Chinese patent document 11 (application number: 201710531296.3) discloses a copper-nickel-silicon alloy and its manufacturing method. In the alloy, the contents of Ni and Si are both 0-2%. The manufacturing method uses a copper source, a nickel source and a silicon source as raw materials, obtains a copper-nickel-silicon alloy slab by melting, continuous casting, cooling, and stretching in this order, and further rolls the copper-nickel-silicon alloy slab in order. , aging, cooling and cold finishing rolling to obtain copper nickel silicon alloy strip.

Also, Chinese Patent Document 11 (Application No.: 200710053838.7) discloses a copper-beryllium-silver alloy and its manufacturing method. The copper alloy material is composed of Cu, BE and AG elements and has a continuous fiber structure. The weight percent content of each component in the alloy material is BE: 0.06-0.12 WT. %, AG 0.08-0.15 WT. % and the rest is Cu. The method of manufacturing the alloy material includes (1) melting the alloy at a temperature of 1180°C to 1200°C, (2) drawing by a continuous direction solidification manufacturing method, and (3) heat treating the material at 700°C to 750°C. Including processing steps.

In addition, Chinese patent document 12 (application number: 201910720284.4) discloses a copper-chromium-zirconium alloy and its manufacturing method. If the material of the alloy is 100% by weight, 15%-20% chromium, 0.2%-0.35% zirconium, 0.02%-0.025% lanthanum, 79.6%-84% Contains 0.5% copper. The specific manufacturing method includes the steps of weighing raw material chromium, raw material zirconia, raw material lanthanum and raw material copper; In addition, a step of covering and melting the surface of the copper liquid, a step of adding and melting zirconium and lanthanum through the material supply port after the chromium is melted, and obtaining a mixed solution after the zirconium and lanthanum are melted. , melted again, melted again, stirred to lower the temperature, flowed into a mold for casting, cooled to obtain an ingot, and solution aging and double deformation aging treatment for the ingot to copper obtaining a chromium-zirconium alloy conductive rod.

In addition, Chinese patent document 13 (application number: 201310633208.2) discloses a copper-chromium multicomponent composite alloy and a method for producing the same. The weight percent ratio of each component in the alloy is 7.5 wt. % to 8.5 wt. % and Al is 0.2 wt. % to 0.4 wt. %, Sn is 0.3 wt. % to 0.5 wt. % and Co is 0.04 wt. % to 0.06 wt. %, Sr is 0.05 wt. % to 0.10 wt. % and the rest is copper. In addition, as a manufacturing method, each component is obtained through treatment steps such as high-temperature melting, cooling, and cooling.

Chinese patent document 14 (application number: 201410474358.8) discloses a copper-titanium composite alloy and a method for producing the same. The weight percent ratio of each component in the copper-titanium alloy material is 3.9 wt. % to 7.8 wt. % and Cr is 1.2 wt. % to 1.8 wt. % and Ca is 0.4 wt. % to 0.9 wt. % and Ni is 0.3 wt. % to 0.8 wt. % and V is 0.2 wt. % to 0.5 wt. % and 0.7 wt. % to 1.2 wt. % and the rest is Cu. The manufacturing method includes processing steps such as melting and cooling in vacuum.

In addition, Chinese patent document 15 (application number: 201510976079.6) discloses a high-strength, high-conductivity copper-chromium-zirconium alloy and its manufacturing method. The chemical composition of the alloy is Cr: 0.01-1.5 wt. %, Zr: 0.01 to 0.5 wt. %, Ti: 0.001 to 0.5 wt. %, Mn: 0.01-0.5 wt. %, Ca: 0.0001 to 0.07 wt. %, the remainder being copper and unavoidable impurities. The flow of the manufacturing method is as follows. Raw material preparation→melting casting→cutting→homogenizing annealing→hot rolling→first solution treatment→milling→first cold rolling→second solution treatment→second cold rolling→first aging treatment→third cold rolling→secondary Aging treatment → tension bending straightening.

In addition, Chinese patent document 16 (application number: 201711414445.4) discloses a method for producing a copper chromium zirconium alloy strip for lead frames. When each component in the copper chromium zirconium alloy strip is weighed according to the weight percentage ratio, the chromium content is 1.0% to 1.5%, the zirconium content is 0.1 to 0.15%, and the silver content is 1.0% to 1.5%. content 0.01-0.015%, cobalt content 0.01-0.015%, beryllium content 0.1-0.15%, titanium 0.1-0.15%, tin 0.1-0.15%, magnesium 0.1-0.15%, niobium 0.1-0.15%, indium 0.1-0.15% and the balance copper. The method for producing the alloy is as follows: up-type continuous casting - continuous extrusion - primary rolling - primary solution treatment - secondary rolling - primary aging - secondary solution treatment - tertiary rolling - secondary It has a process such as secondary aging - quaternary rolling - tertiary aging - finishing.

Chinese Patent Document 17 (Application No.: 201710012956.7) discloses a method for producing precipitation-strengthened high-strength copper-chromium alloys by continuous casting and continuous extrusion. First, using a copper alloy rod formed by horizontal continuous casting, after solution heat treatment on-line, blank material is directly produced by continuous extrusion. Subsequent cold rolling and aging treatments result in finished products meeting performance and dimensional requirements. In the invention according to the document, a high-performance copper-chromium-zirconium alloy material is produced by a continuous extrusion process, and the production process is simplified to some extent, eliminating processes such as milling, hot-rolling opening and blooming, and intermediate The number of rolling passes is reduced, enterprise capital investment is reduced, energy consumption is lowered, and both production efficiency and product yield are improved.

Without listing similar related materials one by one, it can be seen from the previously disclosed materials that research on the composition design of high-strength, high-transmission copper alloys has been extensively conducted, and various alloy compositions have been proposed. . There are various methods for producing high-strength, high-conductivity copper alloys, some of which have already been industrialized. However, these methods are basically the traditional three-stage processing method of copper alloys, ie, molten ingot-hot working-cold working, plus an appropriate heat treatment process. Here, hot working includes hot drawing, hot rolling, hot forging, solution treatment, and the like, and cold working includes cold rolling, cold drawing, and the like. These high-strength and high-conductivity copper alloy production methods require many processes, consume a lot of energy, have a low product rate, large production costs and equipment investment, and the performance of copper alloys must be improved. There is a problem.

Therefore, the main innovation direction of the copper alloy processing industry is to ensure the performance of short process, continuous, energy saving, low input, low cost and high strength and high conductivity of copper alloy.

At present, the production technology of high-strength and high-conductivity copper alloys mainly consists of "up-drawing continuous casting - solution treatment - continuous extrusion - cold rolling", "vacuum melting casting - opening by hot rolling - cold rolling - solidification". There are methods such as "solution-heat treatment" and "horizontal continuous casting-online solution treatment-continuous extrusion-cold rolling-aging treatment". In the production of ingots, horizontal continuous casting is a high-tech continuous casting technology that can provide high quality ingots. However, in any of the existing copper alloy manufacturing methods that introduce the horizontal continuous casting process, it is not possible to obtain an ingot in which all the alloying elements are in a supersaturated solid solution state in the horizontal continuous casting process. It is necessary to further perform a high-temperature solution treatment on the ingot so as to achieve the state, and improvement is still required in terms of energy saving. In addition, existing continuous extrusion processes also generally suffer from premature precipitation and decomposition of supersaturated solid solutions, which affects the strength and electrical conductivity of copper alloys. If you want the material to be in solid solution before aging, the most direct way is to perform a high temperature solution heat treatment before aging, but this idea is not only high in energy consumption but also cold rolling. The hardening effect is also completely lost.

Therefore, in the high-performance copper alloy processing industry, how to make all the alloying elements in the horizontal continuous casting ingot into a supersaturated solid solution state to avoid the subsequent high temperature solid solution, and how to precipitate and decompose the copper alloy solid solution in the continuous extrusion process. To avoid this and ensure high strength and high conductivity of copper alloy is an urgent technical problem to be solved.

A first object of the present invention is to provide a mold material for use in continuous extrusion processes, said mold material having very good mechanical properties.

The second object of the present invention is to provide a continuous extrusion method for high-strength, high-conductivity copper alloys, thereby solving the problem of precipitation and decomposition of supersaturated solid solutions during the continuous extrusion process, and improving the homogeneity and strength of the structure. to improve.

The third object of the present invention is to provide an application of the continuous extrusion method of high strength and high conductivity copper alloy in copper alloy production, thereby shortening the process, reducing energy consumption and cost, and improving product yield. It is to improve the (finished product rate) and ensure the high strength and high conductivity of the copper alloy.

In order to solve the problems existing in the above continuous extrusion method, the present invention uses the following three technical solutions in combination.
1) Employing high temperature preheated extrusion dies and ingots to avoid precipitation and decomposition of supersaturated solid solutions;
2) Continuous extrusion with large extrusion ratios: The use of continuous extrusion parameters with large extrusion ratios not only ensures a sufficiently high deformation temperature to prevent solid solution precipitation, but also violently pushes the ingot into the die cavity. plastically deform and completely destroy the as-cast structure to form a recrystallized structure;
3) Rapid cooling: The blank material is rapidly cooled from high temperature to room temperature by high-intensity cooling to prevent precipitation decomposition of the supersaturated solid solution.

A combination of the above technical means can achieve a dual purpose. First, the uniformity and strength of the structure can be improved by severely plastically modifying the as-cast structure. Second, premature precipitation decomposition of supersaturated solid solutions can be avoided. However, in continuous extrusion at high temperature and high extrusion ratio, both the operating temperature and operating pressure of the die cavity are significantly higher than those in normal continuous extrusion, which is likely to cause extrusion stoppage and mold cracking. Therefore, the output of the extruder must be improved, and the mold of high temperature alloy must be used.

According to a first aspect, the die material used in the continuous extrusion process of the present invention is a forged high temperature nickel-based alloy, the alloy comprising 0.05 wt. % C, 15 wt. % Cr, 6 wt. % Mo, 5 wt. % W, 2 wt. % Ti, 5.5 wt. % Al and the balance Ni, the alloy is melted by vacuum smelting and electroslag remelting methods and then further homogenized before being hot forged and heat treated.

In the present invention, the production of the forged high-temperature nickel-based alloy can refer to the existing technology, specifically, first by melting by vacuum smelting method and electroslag remelting method to obtain an alloy ingot, then , After the alloy ingot is homogenized at 1250 ° C. for 1 to 4 hours, it is formed by isothermal forging at 1000 ° C. to 1050 ° C., and the deformation amount is 80% to 90%, followed by 8 to 16 at 800 ° C. keeping warm for a period of time, quenching with water and quenching, and then tempering at 300° C.-400° C. for 1-2 hours. The wrought high temperature nickel base alloy has very good mechanical properties and can be used as a continuous extrusion die material, especially for the most demanding flag parts.

According to a second aspect, the method for continuously extruding a copper alloy according to the present invention comprises:
(1.1) The extrusion die uses a forged high-temperature nickel-based alloy, which contains 0.05% C, 15% Cr, 6% Mo, 5% W, 2% Ti , 5.5% Al and the balance Ni, the alloy is melted by vacuum smelting and electroslag remelting, and further homogenized before hot forging and heat treatment forming;
(1.2) Before extrusion, the extrusion die is first preheated to 500-600°C, and the copper alloy ingot is rapidly preheated to 700-750°C, then put into the die cavity and continuously extruded to form a blank. Obtaining the material, in which the rotation speed of the extrusion wheel is controlled to 3-8 rpm, the extrusion ratio is 3-8, and the extrusion distance is 0.6-2 mm to ensure a sufficiently high deformation temperature. softening the copper alloy ingot, reducing the deformation resistance and increasing the plastic flowability of the metal, as well as preventing solid solution precipitation in the
(1.3) The blank material obtained in step (1.2) is subjected to high-intensity cooling water spray at the exit of the extrusion die, the spray device uses spray nozzles, and the nozzle spacing is 10-20 mm. Furthermore, the number of nozzles is provided according to the dimensions of the blank material, the distance between the nozzle and the surface of the blank material is 10 to 50 mm, the water pressure is 0.5 to 0.8 Mpa, and the blank material is heated from high temperature to room temperature. preventing precipitation decomposition of the supersaturated solid solution by quenching;
have

In the present invention, the above copper alloy ingot is preferably a copper alloy ingot in which all the alloying elements in the ingot are in a supersaturated solid solution state, and particularly preferably the alloying elements in the ingot obtained directly by horizontal continuous extrusion. are all supersaturated solid solution copper alloy ingots. In this way, not only is it possible to omit the process of high-temperature solutionization, which is the most energy-consuming in the conventional process, but it also provides the possibility of performing subsequent continuous extrusion directly on the ingots obtained by horizontal continuous extrusion. , the process can be shortened, the crystal grains can be effectively refined, and the high strength of the alloy can be ensured.

In order to realize the supersaturated solid solution of the alloying elements in the ingot by horizontal continuous extrusion, the present invention increases the cooling intensity in the horizontal continuous casting process so that the ingot has a very high cooling solidification rate. there is Specifically, the following three technical means ensure high cooling strength in horizontal continuous casting.
(1) Use a multi-channel water-cooled crystallizer. The crystallizer is provided with three sets of independent cooling units along the direction in which the billet is drawn out, realizing multi-channel water supply and multi-channel drainage. In addition, the reverse cooling mode, ie water supply from the cold end and drainage from the hot end, is provided with specific technical parameters to ensure a proper quenching effect.
(2) Rapid cooling increases the viscosity of the molten metal, which may cause casting defects such as billet breakage and holes. Lower to ensure continuous progress of horizontal continuous casting.
(3) Intensive cooling is applied to the billet at the exit of the crystallizer to avoid partial precipitation of solid solution.

Specifically, horizontal continuous casting is preferentially performed as follows. At least one multi-channel water-cooling crystallizer is installed below the side of the heat-retaining furnace, and the multi-channel water-cooling crystallizer is provided with three sets of independent cooling units in sequence along the direction in which the billet is pulled out. It realizes channel water supply and multi-channel drainage. In addition, a reverse cooling mode (ie, water supply from the cold end, drain from the hot end) is employed, with the first set of cooling units closest to the holding furnace. Subsequently, the water inlet temperature of each set of cooling units is set to less than 20° C., and the temperature gradients of the three sets of cooling units are controlled in the following manner. That is, the water flow rate V3 and the cross-sectional area S of the billet of the third set of cooling units satisfy the requirements of 0.5L/(min·mm ² )<V3/S<2L/(min·mm ² ), The water flow rate V2 of the second set of cooling units and the water flow rate V1 of the first set of cooling units are determined so that V1:V2:V3=1.5:1.2:1. Subsequently, electromagnetic induction coils are installed on the outer walls of the water cooling jackets of the cooling units of the first and second sets of the multichannel water-cooled crystallizer to realize electromagnetic stirring, and the electromagnetic stirring mode is rotational stirring. , the frequency of the current is set between 2 and 500 Hz. Subsequently, the cross-sectional area S of the billet is controlled to 2000 to 50 mm ² so that the drawing speed v and the cross-sectional area of the billet satisfy the condition of 0.5 mm·min≦S/v≦20 mm·min. Subsequently, the billet is cooled by installing a water curtain spray cooler within 1000 mm from the exit of the multi-channel water-cooled crystallizer. The spray device uses spray nozzles, the nozzle spacing is 10 to 20 mm, the number of nozzles is provided according to the dimensions of the blank material, the spacing between the nozzle and the surface of the blank material is 10 to 50 mm, and the water pressure is 0. By setting the pressure to 0.5 to 0.8 MPa, all of the alloying elements obtained are supersaturated solid solution copper alloy billets.

In order to achieve high efficiency production, one set of horizontal continuous casting system can be equipped with multiple crystallizers, such as 2-4, to achieve continuous withdrawal (extraction) of 2-4 billets. In this case, the layout mode of the crystallizers is arranged in a row at intervals of 200-400 mm, and each set of crystallizers is provided with an independent water cooling device and an electromagnetic device.

According to a third aspect, the method for continuous pressing of copper alloys according to the invention is used for the production of copper alloys.

Preferably, the above uses are
(a) An as-cast billet of copper alloy is obtained by horizontal continuous casting, and the alloying elements in the as-cast billet are in a supersaturated solid solution state.
(b) stripping the as-cast billet obtained in step (a) for direct continuous extrusion, followed by cold working and aging annealing to obtain a copper alloy;

A copper alloy with high strength and high conductivity can be obtained by subjecting the billet obtained by continuous extrusion according to the present invention to cold working and aging annealing. In other words, continuous extrusion completely destroys the as-cast structure, refines the crystal grains, and superimposes a large number of dislocations generated by cold working to give the alloy a high degree of crystal defects and a high degree of Ensure that it has strength characteristics. After that, aging annealing is performed, using the dislocation cores as fast channels for atomic diffusion, the alloy elements are dispersed and precipitated as second-phase nanoparticles, and the copper matrix is refined to make the alloy highly conductive. It restores modulus and anchors dislocation lines to create a dispersion hardening effect, while releasing cold work deformation energy and avoiding stress cracking. Most importantly, by designing the horizontal continuous casting and continuous extrusion processes described above, the present invention maintains a supersaturated solid solution state of the copper alloy from the casting stage, allowing controlled precipitation only after aging heat treatment. The uniform nature of the solid solution ensures uniform deformation of the material during the intermediate processing steps and improves product yield. At the same time, the precipitation force accumulated in the solid solution is released collectively in a uniform temperature field during the aging heat treatment stage, so it not only has a strong precipitation force, but also the precipitation is controllable, resulting in a uniform precipitation structure. , to ensure performance consistency.

In the present invention, cold rolling, cold drawing, or the like can be employed as cold working. More preferably, the pass deformation amount of cold working is 5% to 10%, and the cumulative deformation amount is 50% to 90%, in order to ensure the deformation amount of cold working. By doing so, in the interior of the blank material, a clear plastic deformation occurs and a large amount of dislocation entanglement is formed.

To ensure complete annealing, the present invention requires an annealing temperature of 300-600° C. and a holding time of 0.5-100 hours. In the present invention, it is particularly preferable to select the annealing temperature and incubation time according to the following principles. That is, blank material samples after cold working were subjected to 0.1, 0.5, 1, 2, 4, 8, 16, 24, 48, Incubate for 99.6 hours. Subsequently, the Vickers hardness (unit: HV) and electrical conductivity (unit: %IACS) of the samples are measured, the product of the hardness value and the electrical conductivity value is calculated, and the test temperature used for the sample with the highest product is and 0.4 h is added to the test time used for the sample with the largest product as the annealing heat retention time of the product.

The copper alloy manufacturing method according to the present invention mainly includes four core steps of horizontal continuous casting, continuous extrusion, cold working, and aging annealing. Other auxiliary steps such as sampling inspection, winding, unwinding, cutting and packaging can be flexibly selected. A typical manufacturing process is as follows. Raw materials are mixed according to the material of the designed product, melted in a horizontal continuous casting furnace, kept warm, and billets are obtained by horizontal continuous casting. Subsequently, the billet is subjected to a peeling treatment. Subsequently, in a continuous extruder, the blank material of preset shape is extruded and then cold worked to preset size, followed by aging annealing and finally cutting and packaging for shipment.

In the present invention, the use described above is particularly preferably carried out according to the following steps.
(1) Preparation and melting of raw materials: The raw materials are prepared according to the composition of the copper alloy, put into the melting furnace and fully melted, and the oxygen content and alloy element content are sampled and analyzed. After the raw materials are replenished according to the above conditions and completely deoxidized, the molten material is put into the heat-retaining furnace through the guide groove inside the melting furnace.

(2) Horizontal continuous casting: Horizontal continuous casting is carried out below the side of the heat-retaining furnace, and at least one multi-channel water-cooling crystallizer is installed below the side of the heat-retaining furnace. The crystallizer is provided with three sets of independent cooling units in sequence along the billet withdrawal direction to realize multi-channel water supply and multi-channel drainage. In addition, the reverse cooling mode is adopted, that is, water is supplied from the cold end and water is discharged from the hot end, and the first set of cooling units is closest to the temperature-retaining furnace. Subsequently, the water inlet temperature of each set of cooling units is set to less than 20°C (a pre-cooling device is required when the actual water temperature exceeds 20°C in summer), and the temperature gradient of the three sets of cooling units is set to: control in such a way. That is, the water flow rate V3 and the cross-sectional area S of the billet of the third set of cooling units satisfy the requirements of 0.5L/(min·mm ² )<V3/S<2L/(min·mm ² ), The water flow rate V2 of the second set of cooling units and the water flow rate V1 of the first set of cooling units are determined so that V1:V2:V3=1.5:1.2:1. This realizes combining the cooling capacities of different intensities of the three sets of cooling units to form a reasonable temperature gradient. Subsequently, electromagnetic induction coils are installed on the outer walls of the water cooling jackets of the cooling units of the first and second sets of the crystallizer to realize electromagnetic stirring. is set between 2 and 500 Hz. Subsequently, the cross-sectional area S of the billet is set to 2000 to 50 mm ² , and the withdrawal (extraction) speed v and the cross-sectional area of the billet satisfy the condition of 0.5 mm·min≦S/v≦20 mm·min. Subsequently, the billet is cooled by installing a water curtain spray cooling device within 1000 mm from the exit of the crystallizer. The spray device uses spray nozzles instead of conventional small hole sprays, the nozzle interval is 10 to 20 mm, the number of nozzles is provided according to the dimensions of the blank material, and the distance between the nozzle and the surface of the blank material is 10. ~50 mm, water pressure 0.5 ~ 0.8 MPa.

(3) Continuous extrusion: A slab obtained by horizontal continuous casting is stripped and then directly continuously extruded. First, the extrusion die is preheated to 500-600° C., and the exfoliated slab is rapidly preheated to 700-750° C. by an on-line induction device, then put into the die cavity of the extrusion die and continuously extruded. The rotation speed of the extrusion wheel is controlled at 3-8 rpm, the extrusion ratio at 3-8, and the extrusion interval at 0.6-2 mm. A high intensity cooling water spray is then applied at the exit of the extrusion die to rapidly cool the blank material from high temperature to room temperature. The spraying device uses atomizing nozzles, the distance between the nozzles is 10-20 mm, and the number of nozzles is provided according to the dimensions of the blank material. The distance between the nozzle and the surface of the blank material is 10-50 mm, and the water pressure is 0.5-0.8 MPa. The material of the extrusion die is high temperature forging containing 0.05% C, 15% Cr, 6% Mo, 5% w, 2% Ti, 5.5% Al and the rest Ni. Nickel-based alloy. The alloy is melted by vacuum smelting and electroslag remelting methods, further homogenized, and shaped by hot forging and heat treatment.

(4) Cold working: Cold working is performed on the billet after continuous extrusion based on the requirements for the product. The pass deformation amount of cold working is 5% to 10%, and the cumulative deformation amount is 50% to 99%.

(5) Aging heat treatment: A cold-worked billet is coiled and placed in a bell-shaped heating furnace for aging heat treatment. First, the billet is placed on the lining, and after the heating furnace body reaches a preset temperature, the lining is lifted and covered so that the billet can heat up quickly. After reaching the preset heat retention time, the furnace body is lifted and moved by a crane to rapidly cool the billet. During heat treatment, a reducing atmosphere is used to prevent oxidation. The product aging temperature and time are determined by the following principles. Multiple sets of cold-treated billet samples were taken at 300, 350, 400, 450, 500, 550, 600°C and , 99.6 h. Subsequently, the Vickers hardness (unit: HV) and electrical conductivity (unit: %IACS) of the samples are measured, the product of the hardness value and the electrical conductivity value is calculated, and the test temperature used for the sample with the highest product is and the product annealing and incubation time is the test time used for the sample with the highest product plus an additional 0.4 h.

(6) Inspect, package and ship.

The copper alloy of the present invention is mainly intended for high-strength and high-transmission copper alloys, especially Cu--X binary alloys, Cu--X--Y ternary alloys and multi-component alloys described in the background art. Suitable for precipitation strengthening of high strength and high conductivity copper alloys such as alloys.

ADVANTAGE OF THE INVENTION According to this invention, there exist the following technical effects.
(1) The continuous extrusion mold material provided by the present invention has very good high temperature mechanical properties, which can greatly extend the life of the mold.

(2) The continuous extrusion method of the present invention avoids premature precipitation and decomposition of a supersaturated solid solution and drastically plastically modifies the as-cast structure, thereby improving the uniformity and strength of the structure and increasing the quality of the copper alloy. Ensure strength and high conductivity.

(3) The horizontal continuous casting of the present invention makes the alloy elements in the billet into a supersaturated solid solution state, which innovates the conventional three-step copper processing process, and can omit the high-temperature solution treatment step, which consumes a lot of energy. The flow has been greatly shortened, and the continuous process of casting, extrusion and cold working has been realized, greatly improving the production speed and increasing the production capacity. In addition, it can effectively refine the grains, improve the uniformity of the microstructure, and ensure high strength of the alloy.

(4) The continuous extrusion of the present invention can maintain the supersaturated solid solution state of the copper alloy, and by utilizing the severe deformation caused by continuous extrusion and the large deformation caused by cold working, the entanglement of high-density dislocations in the solid solution copper matrix generated, ensuring the alloy high strength properties. Then, the dislocation cores are used as fast channels for atomic diffusion to promote the well-dispersed precipitation of alloying elements in the subsequent aging heat treatment to refine the copper matrix and ensure the high electrical conductivity of the copper alloy.

(5) The core idea of the present invention is to maintain the supersaturated solid solution state of the copper alloy from the casting stage and to control precipitation only after the aging heat treatment. The uniform nature of the solid solution ensures uniform deformation of the material during the intermediate processing steps and improves product yield. At the same time, the precipitation force accumulated in the solid solution is released collectively in a uniform temperature field during the aging heat treatment stage, so it not only has a strong precipitation force, but also the precipitation is controllable, resulting in a uniform precipitation structure. , to ensure performance consistency.

1 is a TEM photograph of a copper alloy product according to Example 1, showing Cu-0.5 wt. It shows a large amount of fine Ag precipitate phases inside the %Ag alloy product. It is a metallographic photograph of a cross section of a billet obtained by horizontal continuous casting in Example 1-1, showing a cu-0.5 wt. The equiaxed grain structure of the as-cast structure of the %Ag alloy is shown. FIG. 2 is a view showing the XRD pattern of the billet of Example 1-1 and the XRD pattern of the aging product, showing the supersaturated solid solution structure as a cast billet and the precipitation structure of Ag second phase in the aged state. It is a TEM photograph of a copper alloy product according to Example 4, showing Cu-0.7 wt. %cr-0.15wt. It shows a large amount of fine Cr and Zr precipitate phases inside the %Zr alloy product. It is a metallographic photograph of the billet after continuous extrusion cooling of Example 1-1, showing a recrystallized structure. 1 is a TEM photograph of the billet after continuous extrusion cooling of Example 1-1, showing that no nanoprecipitates are formed in the extruded state, indicating that the properties of a supersaturated solid solution are still maintained. FIG. 2 is a physical photograph of multiple slab failures in the horizontal continuous casting of Examples 1-7, showing that an irrational continuous casting process leads to billet failure. 1 is a TEM photograph of a horizontal continuous cast billet of Example 8, showing premature precipitation of Ag phase due to insufficient cooling. Figure 10 is a physical photograph of the failed extrusion die in Example 9, showing that die steel with good high temperature mechanical properties should be used. 1 is a TEM photograph of the billet after continuous extrusion cooling of Examples 1-9, showing that the supersaturated solid solution precipitates a heterogeneous coarse Ag phase in advance due to insufficient cooling after extrusion. 1 is a TEM photograph of billets after continuous extrusion cooling of Examples 1-13, showing the appearance of Ag precipitates in the structure, indicating partial dissolution of the solid solution. FIG. 11 shows the actual billet drawn from the horizontal continuous casting of Examples 1-15. 1 is a low magnification metallographic photograph of a billet drawn from the horizontal continuous casting of Examples 1-15. 1 is a high magnification metallographic photograph of a billet drawn from the horizontal continuous casting of Examples 1-15, showing no apparent precipitation phases in the particles. FIG. 2 is an XRD pattern diagram of billets drawn from horizontal continuous casting of Examples 1-15, showing only diffraction peaks of copper, no diffraction peaks of the second phase were found, and diffraction peaks and standard When compared with the copper diffraction peak of , the peak value is shifted, indicating that chromium zirconium is dissolved in the copper lattice. 1 is a photograph of the metallographic structure of the billets after continuous extrusion of Examples 1-15, showing an equiaxed crystal structure. 1 is a TEM photograph of the billet after continuous extrusion cooling of Examples 1-15, showing that no nanoprecipitates are formed in the extruded state, indicating that the properties of a supersaturated solid solution are still maintained. 10 is a TEM structure photograph of the slab after cold rolling of Example 25, showing high density dislocation entanglement. FIG. 10 is a TEM structure photograph of the sample after aging treatment of Example 25, showing high density precipitate phases. 10 is a high-resolution TEM structural photograph of the post-aging sample of Example 25, showing a lattice fringe image of the nanoprecipitate phase. 10 is a metallographic photograph of a billet drawn by horizontal continuous casting in Example 26. FIG. Fig. 4 is a metallographic photograph of a billet drawn by horizontal continuous casting of Example 33, with arrows indicating the primary phase of chromium, indicating that chromium formed primary dendrites. Fig. 4 is a physical photograph of the broken billet of horizontal continuous casting of Example 34, the drawing speed and cooling intensity must be reasonably matched, otherwise high efficiency and high quality casting of copper chromium zirconium billet can be achieved. indicates that it is not possible. 1 is a TEM structural photograph of samples after continuous extrusion of Examples 1-23, showing a coarse chromium precipitate phase. Fig. 2 is a structural design drawing of the extrusion die used for continuous extrusion in Examples 1-15 of the present invention, which has a symmetrical structure, the included angle between the AB line and the AD line is 105°, and the CD line and the DA line; The included angle of the line is also 105°, indicating that the length of the diameter of the right semicircle of BC is the length of the BC line segment. It is a structural design drawing of the extrusion die used for continuous extrusion in Example 1-1 of the present invention, the ratio of the diameter d of the circular cavity and the side length a of the die is d / a < 0.5 It shows that

Hereinafter, the technical solutions according to the present invention will be further described with reference to the drawings, but the scope of protection of the present invention is not limited thereto.

(Example 0)
<Production example of forged high-temperature nickel-based alloy>
An alloy ingot was melted by a vacuum smelting method and an electroslag remelting method, and the composition was 0.05 wt. % C, 15 wt. % Cr, 6 wt. % Mo, 5 wt. % W, 2 wt. % Ti, 5.5 wt. % Al and the balance is Ni. The alloy ingots were homogenized at 1250°C for 1 hour and then isothermally forged at 1000°C with a deformation rate of 80%. The alloy was then held at 800° C. for 16 hours, quenched with water, quenched, and then tempered at 350° C. for 1 hour. The tensile properties of the alloys were tested from room temperature to 800°C. Table 1 shows the results.

Table 1 High temperature mechanical properties of alloys

(Example 1-1)
<Step 1: Raw material preparation and melting>
Cu-0.5wt. The raw materials are prepared according to the alloy composition of %Ag, put into the melting furnace and fully melted, the oxygen content and alloy element content are sampled, detected and analyzed. The molten material is completely deoxidized to within 10 minutes, and the molten material is introduced into the heat-retaining furnace through the guide groove in the melting furnace.

<Step 2: Horizontal continuous casting>
Horizontal continuous casting is performed below the side of the holding furnace. Two crystallizers spaced 400 mm apart are installed horizontally below the side of the furnace. The crystallizer is provided with three sets of independent cooling units in sequence along the billet withdrawal direction, and the first set of cooling units is closest to the temperature-retaining furnace. A reverse cooling mode is adopted to keep the water inlet temperature below 20°C. The water flow rate V3 of the third set of cooling units is set at 2000 L/min, the water flow rate V2 of the second set of cooling units is set at 2400 L/min, and the water flow rate V1 of the first set of cooling units is set at 3000 L/min. Electromagnetic stirring was realized by installing an electromagnetic induction coil on the outer wall of the water cooling jacket of the first and second cooling units of the crystallizer. The electromagnetic stirring mode was rotary stirring, and the current frequency was 500 Hz. be. The cross-sectional area S of the billet is 2000 mm ² and the withdrawal (extraction) speed is 100 mm/min. A water curtain is sprayed within a range of 1000 mm from the exit of the crystallizer, 90 spray nozzles are installed, the distance between the spray nozzles is 10 mm, the distance between the nozzle and the surface of the blank material is 10 mm, and the water pressure is 0.8 MPa. get a billet. Fig. 2 shows the fine equiaxed grain structure of the billet, and Fig. 3 shows that the alloying elements of the resulting billet are in a supersaturated solid solution state because no second phase (Ag) is detected by XRD of the billet. indicates that there is

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 500°C. The material for the extrusion die is the forged high temperature nickel base alloy prepared in Example 0. See FIG. 26 for the structural diagram. The slab obtained by horizontal continuous casting is extruded into the die cavity after the surface oxidation defect layer is removed by the stripper, rapidly preheated to 700° C. by the on-line induction device. The rotation speed of the extrusion wheel is controlled at 3 rpm, the extrusion ratio is 3, and the extrusion interval is 0.6 mm. At the exit of the extrusion die, the blank material is sprayed with high-intensity cooling water, and 100 spray nozzles are installed. The distance between the spray nozzles is 10 mm, the distance between the nozzles and the surface of the blank material is 10 mm, the water pressure is 0.8 MPa, and an extruded blank material is obtained. From FIGS. 5 and 6, it can be seen that a recrystallized structure is obtained in the extruded state, there is no second phase inside the crystal grains, and the properties of a supersaturated solid solution are maintained.

(Example 1-2)
<Step 2: Horizontal continuous casting>
Four crystallizers are placed at intervals of 200 mm. The water flow rate V3 of the third set of cooling units is 100 L/min, the water flow rate V2 of the second set of cooling units is 120 L/min, the water flow rate V1 of the first set of cooling units is 150 L/min, and the frequency of electromagnetic stirring is 2 Hz, billet cross-sectional area of 50 mm ² , withdrawal speed of 100 mm/min, spacing of 30 spray nozzles of 20 mm, spacing between nozzles and blank material surface of 50 mm, water pressure of 0.5 MPa.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. 25 spray nozzles are set, the spray nozzle spacing is 20 mm, the spacing between the nozzles and the surface of the blank material is 50 mm, and the water pressure is 0.5 MPa.

Other steps and parameters are the same as in Example 1-1.
Similar to Example 1, the XRD pattern of the billet shows that the billet has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that no nanoprecipitates are formed in the extruded state, indicating that the properties of a supersaturated solid solution are still maintained.

(Example 1-3)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.7wt. %cr-0.15wt. % Zr.

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 600°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Example 1-1.
Here, the XRD pattern of the billet shows that it has the structure of a supersaturated solid solution. A TEM photograph of the billet after extrusion cooling shows the absence of nanoprecipitates in the extruded state, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 1-4)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.7wt. %cr-0.15wt. % Zr.

<Step 2: Horizontal continuous casting>
Three crystallizers are used at 300 mm intervals. The water flow rate V3 of the third set of cooling units is 200 L/min, the water flow rate V2 of the second set of cooling units is 240 L/min, and the water flow rate V1 of the first set of cooling units is 300 L/min. . The electromagnetic stirring frequency is 50 Hz, the cross-sectional area of the billet is 200 mm ² , and the drawing speed is 50 mm/min.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. The extrusion die is preheated to 600°C and the billet is quickly preheated to 700°C.

Other steps and parameters are the same as in Example 1-1.
The XRD pattern of the billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows the absence of nanoprecipitates in the extruded state, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 1-5)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-3wt. % Ni-1 wt. % Si.

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 600°C and quickly preheat the billet to 750°C.

Other steps and parameters are the same as in Example 1-1.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 1-6)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-2wt. % Fe-0.1 wt. %P.

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 550°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Example 1-1.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

According to the results of Examples 1-1 to 1-6, the continuous extrusion method of the present invention is effective for general Cu—X binary alloys (such as Cu—Ag) and Cu—X—Y ternary alloys (Cu— Fe—P, Cu—Cr—Zr, Cu—Ni—Si, etc.).

(Example 1-7)
<Step 3>
The mold material used for continuous extrusion is Cr12MoV mold steel.

Other steps and parameters are the same as in Example 1-1.
Comparing Examples 1-1 and 1-7, if the extrusion die uses normal die steel, the life of the die is very short, the die needs to be replaced frequently, and the production plan Such rhythms are severely damaged, resulting in reduced production capacity and increased waste. FIG. 9 shows a normal die steel plug component that has failed.

(Example 1-8)
<Step 3>
The induction preheating temperature of the continuous extruded billet is 500°C.
Other steps and parameters are the same as in Example 1-1.

(Example 1-9)
<Step 3>
At the outlet of continuous extrusion, spray water-cooled atomizing nozzles are set at intervals of 30 mm, 20 nozzles are set, the distance between the nozzles and the surface of the blank material is 80 mm, and the water pressure is 0.2 MPa.

Other steps and parameters are the same as in Example 1-1.
Comparing Examples 1-1, 1-8, and 1-9, in the continuous extrusion process, when the preheating temperature of the initial billet is low or when the cooling effect of the billet at the extrusion outlet is insufficient, a supersaturated solid solution leads to premature precipitation decomposition of , producing coarse and non-uniform precipitation phases (Fig. 10).

(Example 1-10)
<Step 3>
A continuous extrusion die is preheated to 425°C.

Other steps and parameters are the same as in Example 1-1.
Comparing Examples 1-1 and 1-10, it can be seen that if the die preheat temperature is not sufficient in the continuous extrusion process, the product performance produced in the early stage of extrusion does not reach the level of 120HV & 95% IACS. The reason for this is that the die cavity temperature at the initial stage of extrusion is low and the supersaturated solid solution is prematurely precipitated and decomposed. Also, because the extrusion stress is too high, the life of the mold is shortened.

(Example 1-11)
<Step 3>
The extrusion ratio for continuous extrusion is 1.

Other steps and parameters are the same as in Example 1-1.
Comparing Examples 1-1 and 1-11, it can be seen that if the extrusion ratio is too low in the continuous extrusion process, the deformation of the material is insufficient, the material cannot be effectively strengthened, and the strength of the product is low. . In addition, the extrusion temperature was slightly low, and the supersaturated solid solution was partially precipitated and decomposed early, and the electrical conductivity was slightly impaired.

(Example 1-12)
<Step 3>
The extrusion ratio for continuous extrusion is 9.

Other steps and parameters are the same as in Example 1-1.
Comparing Examples 1-1 and 1-12, if the extrusion ratio is too high in the continuous extrusion process, the product strength will be further improved, but the accident of stopping and breaking the mold will occur many times, causing a serious situation. I know it's happening. Severely impairs equipment service life and production capacity.

(Example 1-13)
<Step 3>
The continuous extrusion outlet is cooled by water tank immersion instead of atomized spray water cooling.

Other steps and parameters are the same as in Example 1-1.

From the comparative analysis of Examples 1-1 and 1-13, if the strong cooling method is not adopted after continuous extrusion,
For example, immersion cooling in the conventional water tank used in Examples 1-13 tends to result in partial precipitation of solid solution, low strength, and weak precipitation force. As shown in FIG. 11, from the TRM after continuous extrusion cooling of the samples of Examples 1-13, it can be observed that the Ag precipitation phase appeared in the microstructure, indicating that the solid solution has already partially precipitated. ing.

(Example 1-14)
<Step 2: High temperature solid solution after normal horizontal continuous casting>
The temperature of the holding furnace is controlled at 1250° C., and a conventional copper inner wall steel sleeve water-cooled crystallizer with only one water-cooling unit is adopted. If the conventional parameters of cooling water flow rate of 50 L/min and traction speed of 10 mm/s are selected, a copper alloy rod is obtained by casting. A copper alloy rod manufactured by horizontal continuous casting is solution treated. The solution treatment temperature was 900° C., the heating mode was online induction heating, and the treatment time was 40 minutes. The quenching adopts the conventional small-hole thermal spraying, setting 90 nozzles, setting the nozzle interval to 30 mm, the distance between the nozzle and the surface of the blank material to 60 mm, and the water pressure to 0.3 MPa.

Other steps and parameters are the same as in Example 1-1. Finally, the billets obtained by continuous extrusion retain supersaturated solid-solution properties and no precipitation phenomenon occurs.

(Example 1-15)
<Step 1: Raw material preparation and melting>
Cu-0.5wt. % Cr-0.1 wt. The raw materials are prepared according to the alloy composition of %Zr, put into the melting furnace and fully melted, and the oxygen content and alloy element content are sampled, detected and analyzed. The molten material is completely deoxidized to within 10 minutes, and the molten material is introduced into the heat-retaining furnace through the guide groove in the melting furnace.

<Step 2: Horizontal continuous casting>
Horizontal continuous casting is performed below the side of the holding furnace. Four crystallizers are installed horizontally at intervals of 200 mm below the side of the heat-retaining furnace. The crystallizer is provided with three sets of independent cooling units in sequence along the billet withdrawal direction, and the first set of cooling units is closest to the temperature-retaining furnace. A reverse cooling mode is adopted to keep the water inlet temperature below 20°C. The water flow rate V3 of the third set of cooling units is set at 50 L/min, the water flow rate V2 of the second set of cooling units is set at 60 L/min, and the water flow rate V1 of the first set of cooling units is set at 75 L/min. Electromagnetic stirring was realized by installing an electromagnetic induction coil on the outer wall of the water cooling jacket of the first and second cooling units of the crystallizer. The electromagnetic stirring mode was rotary stirring, and the current frequency was 2 Hz. be. The cross-sectional area S of the billet is 50 mm ² and the withdrawal (extraction) speed is 100 mm/min. A water curtain is sprayed within a range of 1000 mm from the exit of the crystallizer, 30 spray nozzles are installed, the distance between the spray nozzles is 20 mm, the distance between the nozzle and the surface of the blank material is 50 mm, and the water pressure is 0.5 MPa. .

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 500°C. The extrusion die material is a forged high temperature nickel base alloy prepared in Example 0. See FIG. 25 for the structural drawing of the mold. The slab obtained by horizontal continuous casting is extruded into the die cavity after the surface oxidation defect layer is removed by the stripper, rapidly preheated to 800° C. by the on-line induction device. The rotation speed of the extrusion wheel is controlled at 8 rpm, the extrusion ratio is 8, and the extrusion interval is 2 mm. At the exit of the extrusion die, the blank material is sprayed with high-intensity cooling water, and 20 spray nozzles are installed. The distance between the spray nozzles is 20 mm, the distance between the nozzles and the surface of the blank material is 50 mm, and the water pressure is 0.5 MPa.

FIG. 12 shows a billet rod obtained by horizontal continuous casting in this example. The photographs of the metallographic structure in FIGS. 13 and 14 show that there are no obvious precipitated phases inside the grains. In the XRD diagram of FIG. 15, there are only diffraction peaks for copper and no diffraction peaks for the second phase. A comparison of the diffraction peaks with the standard copper diffraction peaks shows that the peak values are shifted, indicating that the chromium-zirconium element in the resulting billet is in solid solution with the copper lattice. FIG. 16 shows the equiaxed grain structure of the samples after continuous extrusion. FIG. 17 is a TEM photograph of the billet after extrusion cooling, showing the absence of nanoprecipitates in the extruded state, indicating that the properties of a supersaturated solid solution are still maintained.

(Example 1-16)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-1 wt. % Cr-0.15 wt. % Zr.

Other steps and parameters are the same as in Examples 1-15.
Similar to Examples 1-15, the XRD pattern of the as-cast billet shows that it has a supersaturated solid-solution structure, and the TEM photograph of the billet after extrusion cooling shows no nanoprecipitates in the extruded billet. is not produced, indicating that the properties of a supersaturated solid solution are maintained.

(Example 1-17)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.5wt. % Cr-0.1 wt. % Zr-0.05 wt. % Si.

Other steps and parameters are the same as in Examples 1-15.
Similar to Examples 1-15, the XRD pattern of the as-cast billet shows that it has a supersaturated solid-solution structure, and the TEM photograph of the billet after extrusion cooling shows no nanoprecipitates in the extruded billet. is not produced, indicating that the properties of a supersaturated solid solution are maintained.

(Example 1-18)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.5wt. % Cr-0.1 wt. % Zr-0.03 wt. % Mg.

Other steps and parameters are the same as in Examples 1-15.
Similar to Examples 1-15, the XRD pattern of the as-cast billet shows that it has a supersaturated solid-solution structure, and the TEM photograph of the billet after extrusion cooling shows no nanoprecipitates in the extruded billet. is not produced, indicating that the properties of a supersaturated solid solution are maintained.

By comparing and analyzing the results of Examples 1-15 through 1-18, the method of the present invention works well for typical copper-chromium-zirconium ternary alloys and even microalloyed alloys based on copper-chromium-zirconium. It is found to have applicability.

(Example 1-19)
<Step 2: Horizontal continuous casting>
Two crystallizers are placed at a distance of 400 mm. The water flow rate V3 of the third set of cooling units is 500 L/min, the water flow rate V2 of the second set of cooling units is 600 L/min, the water flow rate V1 of the first set of cooling units is 750 L/min, and the frequency of electromagnetic stirring is 500 Hz, billet cross-sectional area of 1000 mm ² , drawing speed of 100 mm/min, spacing of 90 spray nozzles of 10 mm, spacing between nozzles and blank material surface of 10 mm, water pressure of 0.8 MPa.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 3 rpm, the extrusion ratio is 3, and the extrusion spacing is 0.6 mm. 50 spray nozzles are set, the distance between the spray nozzles is 10 mm, the distance between the nozzles and the surface of the blank material is 10 mm, and the water pressure is 0.8 MPa.

Other steps and parameters are the same as in Examples 1-15.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 1-20)
<Step 1: Use three crystallizers at intervals of 300 mm>
The water flow rate V3 of the third set of cooling units is 100 L/min, the water flow rate V2 of the second set of cooling units is 120 L/min, the water flow rate V1 of the first set of cooling units is 150 L/min, and the frequency of electromagnetic stirring is 50 Hz, the cross-sectional area of the billet is 200 mm ² , and the drawing speed is 50 mm/min.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. Preheat the extrusion die to 600°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Examples 1-15.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 1-21)
<Step 3: Continuous Extrusion>
Preheat the extrusion die to 550°C and quickly preheat the billet to 750°C.

Other steps and parameters are the same as in Examples 1-15.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 1-22)
<Step 3>
The induction preheating temperature of the continuous extruded billet is 600°C.
Other steps and parameters are the same as in Examples 1-15.

(Example 1-23)
<Step 3>
A spray water-cooled atomizing nozzle is set at an interval of 30 mm at the outlet of the continuous extrusion, the interval between the nozzle and the surface of the blank material is 80 mm, and the water pressure is 0.2 MPa.

Other steps and parameters are the same as in Examples 1-15.
Comparing Examples 1-15, 1-22, and 1-23, in the continuous extrusion process, when the initial billet preheating temperature is low or when the billet cooling effect at the extrusion outlet is insufficient, all supersaturated solid solutions leads to premature precipitation decomposition of , producing coarse and non-uniform precipitation phases (Fig. 24).

(Example 1-24)
<Step 3>
A continuous extrusion die is preheated to 450°C.

Other steps and parameters are the same as in Examples 1-15.
Comparing Examples 1-15 and 1-24, it can be seen that in a continuous extrusion process, if the die preheat temperature is not sufficient, the product performance produced in the early stages of extrusion does not reach the level of 200HV & 84% IACS. The reason for this is that the die cavity temperature at the initial stage of extrusion is low and the supersaturated solid solution is prematurely precipitated and decomposed. Also, because the extrusion stress is too high, the life of the mold is shortened.

(Example 1-25)
<Step 3>
The extrusion ratio for continuous extrusion is two.

Other steps and parameters are the same as in Examples 1-15.
Comparing Examples 1-15 and 1-25, it can be seen that if the extrusion ratio is too low in the continuous extrusion process, the deformation of the material is insufficient, the material cannot be strengthened effectively, and the strength of the product is low. . In addition, the extrusion temperature was slightly low, and the supersaturated solid solution was dissolved and decomposed in advance, and the electrical conductivity was slightly impaired.

(Example 1-26)
<Step 3>
The extrusion ratio for continuous extrusion is 10.

Other steps and parameters are the same as in Examples 1-15.
Comparing Examples 1-15 and 1-26, if the extrusion ratio is too high in the continuous extrusion process, although the product strength is further improved, stoppages and mold destruction accidents occur many times, causing serious problems. I know it's happening. Severely impairs equipment service life and production capacity.

(Example 1-28)
<Step 2: High temperature solid solution after normal horizontal continuous casting>
The temperature of the holding furnace is controlled at 1250° C., and the crystallizer adopts a conventional copper inner wall steel sleeve water-cooling crystallizer with only one cooling device. The cooling water flow rate is 50 L/min as the conventional parameters, and the traction speed is 10 mm/s. Copper alloy bars are obtained by casting. A copper alloy rod manufactured by horizontal continuous casting is solution treated. The solution treatment temperature was 900° C., the heating mode was online induction heating, and the treatment time was 40 minutes. The quenching adopts the conventional small-hole thermal spraying, setting 90 nozzles, setting the nozzle interval to 30 mm, the distance between the nozzle and the surface of the blank material to 60 mm, and the water pressure to 0.3 MPa.

Other steps and parameters are the same as in Examples 1-25. Finally, the billets obtained by continuous extrusion retain supersaturated solid-solution properties and no precipitation phenomenon occurs.

(Example 1)
<Step 1: Raw material preparation and melting>
Cu-0.5wt. The raw materials are prepared according to the alloy composition of %Ag, put into the melting furnace and fully melted, the oxygen content and alloy element content are sampled, detected and analyzed. The molten material is completely deoxidized to within 10 minutes, and the molten material is introduced into the heat-retaining furnace through the guide groove in the melting furnace.

<Step 2: Horizontal continuous casting>
Horizontal continuous casting is performed below the side of the holding furnace. Four crystallizers are installed horizontally at intervals of 400 mm below the side of the heat-retaining furnace. The crystallizer is provided with three sets of independent cooling units in sequence along the billet withdrawal direction, and the first set of cooling units is closest to the temperature-retaining furnace. A reverse cooling mode is adopted to keep the water inlet temperature below 20°C. The water flow rate V3 of the third set of cooling units is set at 2000 L/min, the water flow rate V2 of the second set of cooling units is set at 2400 L/min, and the water flow rate V1 of the first set of cooling units is set at 3000 L/min. Electromagnetic stirring was realized by installing an electromagnetic induction coil on the outer wall of the water cooling jacket of the first and second cooling units of the crystallizer. The electromagnetic stirring mode was rotary stirring, and the current frequency was 500 Hz. be. The cross-sectional area S of the billet is 2000 mm ² and the withdrawal (extraction) speed is 100 mm/min. A water curtain is sprayed within a range of 1000 mm from the outlet of the crystallizer, 90 spray nozzles are installed, the distance between the spray nozzles is 10 mm, the distance between the nozzle and the surface of the blank material is 10 mm, and the water pressure is 0.8 MPa. .

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 500°C. The material for the extrusion die is the forged high temperature nickel base alloy prepared in Example 0. See FIG. 26 for the structural diagram. The slabs obtained by horizontal continuous casting are stripped of the surface oxidation defect layer by a peeler, rapidly preheated to 700° C. by an on-line induction device, then entered into the die cavity and extruded. The rotation speed of the extrusion wheel is controlled at 3 rpm, the extrusion ratio is 3, and the extrusion interval is 0.6 mm. At the exit of the extrusion die, the blank material is sprayed with high-intensity cooling water, and 100 spray nozzles are installed. The distance between the spray nozzles is 10 mm, the distance between the nozzles and the surface of the blank material is 10 mm, and the water pressure is 0.8 MPa.

<Step 4: Cold drawing>
Cold drawing the extruded blank material according to product requirements. The pass deformation amount of cold drawing is 5%, and the cumulative deformation amount is 50%.

<Step 5: Aging heat treatment>
The cold-worked billet is coiled and placed in a bell-shaped heating furnace for aging heat treatment. First, the billet is placed on the lining, and after the heating furnace body reaches a preset temperature, the lining is lifted and covered so that the billet can heat up rapidly. After reaching the preset heat retention time, the furnace body is lifted and moved by a crane to rapidly cool the billet. During heat treatment, a reducing atmosphere is used to prevent oxidation. The product aging temperature and time are determined by the following principles. Multiple sets of cold-treated billet samples were taken at 300, 350, 400, 450, 500, 550, 600°C and , 99.6 h. Subsequently, the Vickers hardness (unit: HV) and electrical conductivity (unit: %IACS) of the samples are measured, the product of the hardness value and the electrical conductivity value is calculated, and the test temperature used for the sample with the highest product is and the product annealing and incubation time is the test time used for the sample with the highest product plus an additional 0.4 h. The results show that the sample has the maximum product value after annealing at 400° C. for 1 h, taking 400° C. as the temperature for keeping the product and 1.4 h for the keeping time of the product.

<Step 6>
A Vickers hardness tester is used to measure the Vickers hardness of the product, and an eddy current conductivity tester is used to measure the electrical conductivity of the product. See Table 2 for results.

It can be seen from FIGS. 1 and 4 that dispersed nanoprecipitates and high density sites are produced in the copper alloy of this example. The fine and dense equiaxed crystal structure of the cast billet can be seen from FIG. From FIG. 3, the XRD of the cast billet did not detect the second phase (Ag), whereas the XRD of the aging product detected a clear diffraction peak of the second phase. characteristics and the precipitation phase strengthening structure in the aging mode have been proved. From FIGS. 5 and 6, it can be seen that a recrystallized structure is obtained in the extruded state, there is no second phase in the crystal grains, and the properties of a supersaturated solid solution are maintained.

(Example 2)
<Step 2: Horizontal continuous casting>
Four crystallizers are used with an interval of 200 mm, the water flow rate V3 of the third set of cooling units is 100 L/min, the water flow rate V2 of the second set of cooling units is 120 L/min, and the water flow rate of the first set of cooling units is The water flow rate V1 is 150 L/min, the frequency of electromagnetic stirring is 2 Hz, the cross-sectional area of the billet is 50 mm ² , the withdrawal speed is 100 mm/min, the interval between the 30 spray nozzles is 20 mm, and the interval between the nozzles and the surface of the blank material is 50 mm, water pressure is 0.5 MPa.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. 25 spray nozzles are set, the spray nozzle spacing is 20 mm, the spacing between the nozzles and the surface of the blank material is 50 mm, and the water pressure is 0.5 MPa.

<Step 4: Cold working>
The amount of deformation for each pass is 10%, and the cumulative amount of deformation is 99%.

Other steps and parameters are the same as in Example 1.
Similar to Example 1, the XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure, and the TEM photograph of the billet after extrusion cooling shows that no nanoprecipitates are formed in the extruded billet and supersaturated It shows that the properties of solid solution are still maintained.

(Example 3)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.7wt. % Cr-0.15 wt. % Zr.

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 600°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Example 1.
Here, an XRD diagram of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 4)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.7wt. % Cr-0.15 wt. % Zr.

<Step 2: Horizontal continuous casting>
Three crystallizers are used at 300 mm intervals. The water flow rate V3 of the third set of cooling units is 200 L/min, the water flow rate V2 of the second set of cooling units is 240 L/min, and the water flow rate V1 of the first set of cooling units is 300 L/min. . The electromagnetic stirring frequency is 50 Hz, the cross-sectional area of the billet is 200 mm ² , and the drawing speed is 50 mm/min.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. Preheat the extrusion die to 600°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Example 1.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution. It can be seen from FIG. 4 that the copper alloy produced in this example produced dispersed nanoprecipitates and a high density of dislocations.

(Example 5)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-3wt. % Ni-1 wt. % Si.

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 600°C and quickly preheat the billet to 750°C.

Other steps and parameters are the same as in Example 1.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 6)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-2wt. % Fe-0.1 wt. %P.

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 550°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Example 1.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 7)
<Step 2: Horizontal continuous casting>
Four crystallizers are used with a spacing of 200 mm, the water flow rate V3 of the third set of cooling units is 100 L/min, the water flow rate V2 of the second set of cooling units is 120 L/min, the first set is 150 L/min. The electromagnetic stirring frequency is 2 Hz, the cross-sectional area of the billet is 50 mm ² , and the drawing speed is 200 mm/min. The distance between the 30 spray nozzles is 10 mm, the distance between the nozzles and the surface of the blank material is 10 mm, and the water pressure is 0.8 MPa.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. The distance between the spray nozzles is 20 mm, the distance between the nozzles and the surface of the blank material is 50 mm, and the water pressure is 0.5 MPa.

<Step 4: Cold working>
The amount of deformation for each pass is 10%, and the cumulative amount of deformation is 99%.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 7, for small cross-section billets, employing higher withdrawal speeds and more intense spray cooling improved the cooling effect and resulted in rapid solidification despite sufficient solid solution. and breakage of the billet (Fig. 7), and the continuity of production is greatly reduced.

(Example 8)
<Step 2: Horizontal continuous casting>
The electromagnetic stirring frequency is 2 Hz, the withdrawal speed is 50 mm/min, and the water pressure is 0.2 MPa.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 8, it can be seen that when the drawing speed is slow, the electromagnetic stirring frequency is low, and the cooling water pressure is low, the copper alloy melt is sufficiently stirred to form fine equiaxed crystals. Ag atoms prematurely precipitate from the supersaturated solid solution and evolve into a coarse primary phase (Fig. 8). The strength of the alloy is weakened, subsequent precipitation is poor, and the electrical conductivity of the alloy is compromised. Therefore, it is necessary to rationally combine process parameters such as drawing cross-sectional area, drawing speed, cooling water pressure, and electromagnetic stirring frequency.

(Example 9)
<Step 3>
The mold material used for continuous extrusion is Cr12MoV mold steel.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 9, if the extrusion die uses ordinary die steel, the life of the die is very short, and the die needs to be replaced frequently, which seriously damages the production rhythm. - Adds cost, reduces production capacity and increases waste. FIG. 9 shows a typical discarded die steel plug piece.

(Example 10)
<Step 3>
The induction preheating temperature of the continuous extruded billet is 500°C.
Other steps and parameters are the same as in Example 1.

(Example 11)
<Step 3>
At the outlet of continuous extrusion, spray water-cooled atomizing nozzles are set at intervals of 30 mm, 20 nozzles are set, the distance between the nozzles and the surface of the blank material is 80 mm, and the water pressure is 0.2 MPa.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1, 10, and 11, in the continuous extrusion process, if the billet preheat temperature is low or the billet cooling effect at the extrusion exit is insufficient, the product strength and premature precipitation decomposition of the supersaturated solid solution will lead to electrical conductivity. The modulus drops and a coarse and non-uniform precipitate phase occurs (Fig. 10).

(Example 12)
<Step 3>
A continuous extrusion die is preheated to 425°C.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 12, it can be seen that if the die preheat temperature is not sufficient in the continuous extrusion process, the performance of the product produced in the early stages of extrusion does not reach the level of 120HV & 95% IACS. The reason for this is that the die cavity temperature at the initial stage of extrusion is low and the supersaturated solid solution is precipitated and decomposed in advance. Also, because the extrusion stress is too high, the life of the mold is shortened.

(Example 13)
<Step 3>
The extrusion ratio for continuous extrusion is 1.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 13, it can be seen that if the extrusion ratio is too low in the continuous extrusion process, the deformation of the material is insufficient, the material cannot be effectively strengthened, and the strength of the product is low. In addition, the extrusion temperature was slightly low, and the supersaturated solid solution was dissolved and decomposed in advance, and the electrical conductivity was slightly impaired.

(Example 14)
<Step 3>
The extrusion ratio for continuous extrusion is 9.

Other steps and parameters are the same as in Example 1.
Comparing Example 1 and Example 14, if the extrusion ratio is too high in the continuous extrusion process, the product strength will be further improved, but the accident of stopping and breaking the mold will occur many times, causing serious problems. I know there is. Severely impairs equipment service life and production capacity.

(Example 15)
<Step 4>
The cumulative deformation amount of cold working is 30%.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 15, it can be seen that when the cumulative deformation amount of cold working is small, the work hardening effect of the copper alloy is weak, the dislocation density is not high, and the precipitation force is weak. Not only does it have low hardness, but it also has low conductivity.

(Example 16)
<Step 5: Aging heat treatment>
The sample is annealed at 400° C. for 1 hour.

Other steps and parameters are the same as in Example 1.
By comparing Examples 1 and 16, it can be seen that, when selecting the aging annealing heat retention time, unless 0.4 hours necessary for the present invention is added, the alloying elements cannot be completely precipitated during aging, and the conductivity is reduced. It can be seen that the rate is lower. The 0.4 h addition is a detailed rule formulated with careful consideration of large furnace charges and differences in temperature rise and average temperature characteristics of small samples.

(Example 17)
<Step 2>
The water flow rate V3 of the third set of cooling units is 4000 L/min, the water flow rate V2 of the second set of cooling units is 4800 L/min, and the water flow rate V1 of the first set of cooling units is 6000 L/min.
Other steps and parameters are the same as in Example 1.

(Example 18)
<Step 2>
The water flow rate V3 of the third set of cooling units is 1000 L/min, the water flow rate V2 of the second set of cooling units is 1200 L/min, and the water flow rate V1 of the first set of cooling units is 1500 L/min.
Other steps and parameters are the same as in Example 1.

(Example 19)
<Step 2>
The water flow rate V3 of the third set of cooling units is 6000 L/min, the water flow rate V2 of the second set of cooling units is 7200 L/min, and the water flow rate V1 of the first set of cooling units is 12000 L/min.
Other steps and parameters are the same as in Example 1.

(Example 20)
<Step 2>
The water flow rate V3 of the third set of cooling units is 500 L/min, the water flow rate V2 of the second set of cooling units is 600 L/min, and the water flow rate V1 of the first set of cooling units is 1000 L/min.
Other steps and parameters are the same as in Example 1.

Through comparative analysis of Examples 1, 17, 18, 19 and 20, good high It can be seen that a strong and highly conductive copper alloy is obtained. If the water flow rate is too high (as in Example 19), the cooling will be too strong and the metal will solidify directly on the inner wall of the mold, causing clogging and impeding proper extraction. If the water flow is too low (as in Example 20) there is insufficient cooling to ensure that the billet is in solid solution and some of the Ag precipitates prematurely, reducing strength and conductivity.

(Example 21)
<Step 2>
The water flow rate V3 of the third set of cooling units is 2000 L/min, the water flow rate V2 of the second set of cooling units is 2000 L/min, and the water flow rate V1 of the first set of cooling units is 2000 L/min.
Other steps and parameters are the same as in Example 1.

Comparative analysis of Examples 1 and 21 shows that if the water flow rates of the three cooling units of the mold are not set according to the ratios disclosed in the present invention, a reasonable cooling gradient cannot be formed in the three cooling units. I understand. The inner walls of the mold wear significantly, reducing the service life by 50%.

(Example 22)
<Step 3>
The continuous extrusion outlet is cooled by water tank immersion instead of atomized spray water cooling.
Other steps and parameters are the same as in Example 1.

By comparative analysis of Example 1 and Example 22, if a strong cooling method is not adopted after continuous extrusion, such as the conventional immersion cooling in a water tank used in Example 22, the solid solution is likely to partially precipitate, and the strength is compared. It can be seen that the precipitation power is weak. As shown in FIG. 11, the temperature of the sample of Example 22 after continuous extrusion cooling observed that the Ag precipitation phase appeared in the structure, indicating that the solid solution was partially precipitated.

(Example 23)
<Step 2>
A conventional small hole spray is adopted for the first billet spray, 90 nozzles are set, the nozzle spacing is 30 mm, the spacing between the nozzle and the billet surface is 60 mm, and the water pressure is 0.3 MPa.

Other steps and parameters are the same as in Example 1.
From the comparative analysis of Examples 1 and 23, it can be seen that if a powerful cooling method is not adopted when the billet is continuously withdrawn, such as the conventional small hole thermal spraying used in Example 23, the water pressure and inter-hole distance are unreasonable. , which can lead to partial precipitation of solid solutions, low strength, and weak analytical power.

(Example 24)
<Step 2: High temperature solid solution after normal horizontal continuous casting>
The temperature of the holding furnace is controlled at 1250° C., and a conventional copper inner wall steel sleeve water-cooled crystallizer with only one water-cooling unit is adopted. The cooling water flow rate is 50 L/min as conventional parameters, and the traction speed is 10 mm/sec. Copper alloy bars are obtained by casting. A copper alloy rod manufactured by horizontal continuous casting is solution treated. The solution treatment temperature was 900° C., the heating mode was online induction heating, and the treatment time was 40 minutes. The quenching adopts the conventional small-hole thermal spraying, setting 90 nozzles, setting the nozzle interval to 30 mm, the distance between the nozzle and the surface of the blank material to 60 mm, and the water pressure to 0.3 MPa.

Other steps and parameters are the same as in Example 1.
Comparing Examples 1 and 24, compared to the conventional horizontal continuous casting + hot solid solution technology, the product of the present invention has significantly improved both hardness and electrical conductivity, and the high temperature solid solution step, which is a high energy consumption step. It can be seen that no solubilization is required.

＊ １セットの水平連続鋳造＋連続押出生産ラインの容量のみがカウントされる Table 2 summarizes the product performance, yield and capacity of the examples.

* Only the capacity of one set of horizontal continuous casting + continuous extrusion production line is counted

(Example 25)
<Step 1: Raw material preparation and melting>
Cu-0.5wt. % Cr-0.1 wt. The raw materials are prepared according to the alloy composition of %Zr, put into the melting furnace and fully melted, and the oxygen content and alloy element content are sampled, detected and analyzed. The molten material is completely deoxidized to within 10 minutes, and the molten material is introduced into the heat-retaining furnace through the guide groove in the melting furnace.

<Step 2: Horizontal continuous casting>
Horizontal continuous casting is performed below the side of the holding furnace. Four crystallizers spaced 200 mm apart are installed horizontally below the side of the heat-retaining furnace. The crystallizer is provided with three sets of independent cooling units in sequence along the billet withdrawal direction, and the first set of cooling units is closest to the temperature-retaining furnace. A reverse cooling mode is adopted to keep the water inlet temperature below 20°C. The water flow rate V3 of the third set of cooling units is set at 50 L/min, the water flow rate V2 of the second set of cooling units is set at 60 L/min, and the water flow rate V1 of the first set of cooling units is set at 75 L/min. Electromagnetic stirring was realized by installing an electromagnetic induction coil on the outer wall of the water cooling jacket of the first and second cooling units of the crystallizer. The electromagnetic stirring mode was rotary stirring, and the current frequency was 2 Hz. be. The cross-sectional area S of the billet is 50 mm ² and the withdrawal (extraction) speed is 100 mm/min. A water curtain is sprayed within a range of 1000 mm from the outlet of the crystallizer, 30 spray nozzles are installed, the distance between the spray nozzles is 20 mm, the distance between the nozzle and the surface of the blank material is 50 mm, and the water pressure is 0.5 Pa. .

<Step 3: Continuous Extrusion>
Preheat the extrusion die to 500°C. The extrusion die material is the forged high temperature nickel base alloy prepared in Example 0. See FIG. 26 for the structural diagram. The slab obtained by horizontal continuous casting is extruded into the die cavity after the surface oxidation defect layer is removed by the stripper, rapidly preheated to 800° C. by the on-line induction device. The rotation speed of the extrusion wheel is controlled at 8 rpm, the extrusion ratio is 8, and the extrusion interval is 2 mm. At the exit of the extrusion die, the blank material is sprayed with high-intensity cooling water, and 20 spray nozzles are installed. The distance between the spray nozzles is 20 mm, the distance between the nozzles and the surface of the blank material is 50 mm, and the water pressure is 0.5 MPa.

<Step 4: Cold rolling>
Cold rolling the extruded blank material according to product requirements. The pass deformation amount of cold rolling is 5%, and the cumulative deformation amount is 99%.

<Step 5: Aging heat treatment>
A cold-rolled billet is coiled and placed in a bell-shaped heating furnace for aging heat treatment. First, the billet is placed on the lining, and after the heating furnace body reaches a preset temperature, the lining is lifted and covered so that the billet can heat up rapidly. After reaching the preset heat retention time, the furnace body is lifted and moved by a crane to rapidly cool the billet. During heat treatment, a reducing atmosphere is used to prevent oxidation. The product aging temperature and time are determined by the following principles. Multiple sets of cold-treated billet samples were taken at 300, 350, 400, 450, 500, 550, 600°C and , 99.6 h. Subsequently, the Vickers hardness (unit: HV) and electrical conductivity (unit: %IACS) of the samples are measured, the product of the hardness value and the electrical conductivity value is calculated, and the test temperature used for the sample with the highest product is and the product annealing and incubation time is the test time used for the sample with the highest product plus an additional 0.4 h. As a result, it has the maximum product value after annealing at 500° C. for 1 hour, indicating that the temperature for keeping the product is 500° C. and the time for keeping the product is 1.4 hours.

<Step 6>
A Vickers hardness tester is used to measure the Vickers hardness of the product, and an eddy current conductivity tester is used to test the electrical conductivity of the product. See Table 3 for results.

FIG. 12 shows a billet rod obtained by horizontal continuous casting in this example. The photographs of the metallographic structure in FIGS. 13 and 14 show that there are no obvious precipitated phases inside the grains. In the XRD diagram of FIG. 15, there are only diffraction peaks for copper and no diffraction peaks for the second phase. A comparison of the diffraction peaks with the standard copper diffraction peaks shows that the peak values are shifted, indicating that the chromium-zirconium element in the resulting billet is in solid solution with the copper lattice. FIG. 16 shows the equiaxed grain structure of the samples after continuous extrusion. FIG. 17 is a TEM photograph of the billet after extrusion cooling, showing the absence of nanoprecipitates in the extruded state, indicating that the properties of a supersaturated solid solution are still maintained. FIG. 18 shows that there is a high density of dislocation entanglements in the cold rolled sample. FIG. 19 shows the appearance of dense precipitates inside the aged sample. FIG. 20 shows a checkered image of nanoprecipitates by high-resolution TEM.

(Example 26)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-1 wt. %cr-0.15wt. % Zr.

Other steps and parameters are the same as in Example 25.
Similar to Example 25, the XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure, and the TEM photograph of the billet after extrusion cooling shows the formation of nanoprecipitates in the extruded billet. , indicating that the properties of a supersaturated solid solution are maintained.

(Example 27)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.5wt. % Cr-0.1 wt. % Zr-0.05 wt. % Si.

Other steps and parameters are the same as in Example 25.
Similar to Example 25, the XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure, and the TEM photograph of the billet after extrusion cooling shows the formation of nanoprecipitates in the extruded billet. , indicating that the properties of a supersaturated solid solution are maintained.

(Example 28)
<Step 1: Raw material preparation and melting>
The alloy composition is Cu-0.5wt. % Cr-0.1 wt. % Zr-0.03 wt. % Mg.

Other steps and parameters are the same as in Example 25.
Similar to Example 25, the XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure, and the TEM photograph of the billet after extrusion cooling shows the formation of nanoprecipitates in the extruded billet. , indicating that the properties of a supersaturated solid solution are maintained.

By comparing and analyzing the results of Examples 25 to 28, the method of the present invention has good applicability to typical copper chromium zirconium ternary alloys and further microalloyed alloys based on copper chromium zirconium. I understand. The fabricated copper chromium zirconium plates and strips have a fine and uniform nanoprecipitate phase structure, high strength and high electrical conductivity. Its comprehensive performance is close to or better than that obtained by other technologies and has high yields. Ideal for industrial large scale manufacturing.

(Example 29)
<Step 2: Horizontal continuous casting>
Two crystallizers are placed at a distance of 400 mm. The water flow rate V3 of the third set of cooling units is 500 L/min, the water flow rate V2 of the second set of cooling units is 600 L/min, the water flow rate V1 of the first set of cooling units is 750 L/min, and the frequency of electromagnetic stirring is 500 Hz, billet cross-sectional area of 1000 mm ² , drawing speed of 100 mm/min, spacing of 90 spray nozzles of 10 mm, spacing between nozzles and blank material surface of 10 mm, water pressure of 0.8 MPa.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 3 rpm, the extrusion ratio is 3, and the extrusion spacing is 0.6 mm. 50 spray nozzles are set, the distance between the spray nozzles is 10 mm, the distance between the nozzles and the surface of the blank material is 10 mm, and the water pressure is 0.8 MPa.

Other steps and parameters are the same as in Example 25.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 30)
<Step 1: Use three crystallizers at intervals of 300 mm>
The water flow rate V3 of the third set of cooling units is 100 L/min, the water flow rate V2 of the second set of cooling units is 120 L/min, the water flow rate V1 of the first set of cooling units is 150 L/min, and the frequency of electromagnetic stirring is 50 Hz, the cross-sectional area of the billet is 200 mm ² , and the drawing speed is 50 mm/min.

<Step 3: Continuous Extrusion>
The extrusion wheel speed is 8 rpm, the extrusion ratio is 8, and the extrusion spacing is 2 mm. Preheat the extrusion die to 600°C and quickly preheat the billet to 700°C.

Other steps and parameters are the same as in Example 25.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 31)
<Step 3: Continuous Extrusion>
Preheat the extrusion die to 550°C and quickly preheat the billet to 750°C.

Other steps and parameters are the same as in Example 25.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 32)
<Step 4>
The cumulative deformation amount of cold rolling is 50%.

Other steps and parameters are the same as in Example 25.
An XRD pattern of the as-cast billet shows that it has a supersaturated solid solution structure. A TEM photograph of the billet after extrusion cooling shows that the extruded billet is free of nanoprecipitates, indicating that it still maintains the properties of a supersaturated solid solution.

(Example 33)
<Step 2: Horizontal continuous casting>
The electromagnetic stirring frequency is 1 Hz, the withdrawal speed is 2 mm/min, and the water pressure is 0.2 MPa.

Other steps and parameters are the same as in Example 25.
Comparing Examples 25 and 33, it can be seen that the melt of the copper chromium zirconium plate and strip cannot be sufficiently agitated into fine particles when the withdrawal speed is low, the electromagnetic agitation frequency is low, and the cooling water pressure is low. . Equiaxed crystals and some Ag atoms prematurely precipitate from the supersaturated solid solution and evolve into a coarse primary phase (Fig. 22). The strength of the alloy is weakened, subsequent precipitation is poor, and the electrical conductivity of the alloy is compromised.

(Example 34)
<Step 2: Horizontal continuous casting>
The withdrawal speed is 400 mm/min and the water pressure is 1.0 MPa.

Other steps and parameters are the same as in Example 25.
Comparing Examples 25 and 34, for small cross-section billets, higher withdrawal speed combined with more intense spray cooling improves the cooling effect and solid solution is sufficient, but rapid solidification and This leads to breakage of the billet (Fig. 23), causing great damage to the continuity of production.

Comparing Examples 25, 33, and 34, a rational combination of process parameters such as drawing cross-sectional area, drawing speed, cooling water pressure, and electromagnetic stirring frequency is required to obtain high-efficiency, high-quality copper-chromium-zirconium billets. you know you need it.

(Example 35)
<Step 3>
The induction preheating temperature of the continuous extruded billet is 600°C.
Other steps and parameters are the same as in Example 25.

(Example 36)
<Step 3>
A spray water-cooled atomizing nozzle is 30 mm away from the outlet of the continuous extrusion, the distance between the nozzle and the surface of the blank material is 80 mm, and the water pressure is 0.2 MPa.

Other steps and parameters are the same as in Example 25.
Comparing Examples 25, 35, and 36, in the continuous extrusion process, if the billet preheat temperature is low or the billet cooling effect at the extrusion outlet is insufficient, the product strength and premature precipitation decomposition of the supersaturated solid solution will lead to electrical conductivity. modulus is reduced and a coarse and non-uniform precipitate phase occurs (Fig. 24).

(Example 37)
<Step 3>
A continuous extrusion die is preheated to 450°C.

Other steps and parameters are the same as in Example 25.

Comparing Examples 25 and 37, it can be seen that the performance of the product produced in the early stages of extrusion does not reach the level of 200HV & 84% IACS if the die preheat temperature is not sufficient in the continuous extrusion process. The reason for this is that the supersaturated solid solution is prematurely precipitated and decomposed due to the low die cavity temperature at the initial stage of extrusion. Also, because the extrusion stress is too high, the life of the mold is shortened.

(Example 38)
<Step 3>
The extrusion ratio for continuous extrusion is two.

Other steps and parameters are the same as in Example 25.
Comparing Examples 25 and 38, it can be seen that if the extrusion ratio is too low in the continuous extrusion process, the deformation of the material is insufficient to effectively strengthen the material and the strength of the product is low. In addition, the extrusion temperature was slightly low, and the supersaturated solid solution was precipitated and decomposed in advance, and the electrical conductivity was slightly impaired.

(Example 39)
<Step 3>
The extrusion ratio for continuous extrusion is 10.

Other steps and parameters are the same as in Example 25.
Comparing Example 25 and Example 39, if the extrusion ratio is too high in the continuous extrusion process, the product strength will be further improved, but there will be many stoppages and mold breakage accidents, and serious problems will occur. I know there is. Severely impairs equipment service life and production capacity.

(Example 40)
<Step 4>
The cumulative deformation amount of cold rolling is 40%.

Other steps and parameters are the same as in Example 25.
Comparing Example 25 and Example 40, it can be seen that the cumulative deformation amount of cold rolling is small, the work hardening effect of the copper chromium zirconium plate and strip is weak, the dislocation density is not high, and the precipitation force is weak. Not only does it have low hardness, but it also has low conductivity.

(Example 41)
<Step 5: Aging heat treatment>
The sample is annealed at 500°C for 1 hour.

Other steps and parameters are the same as in Example 25.
By comparing Examples 25 and 41, it can be seen that if the 0.4 hour required for the present invention is not added when selecting the aging annealing holding time, the alloying elements cannot be fully aged and precipitated, and the electrical conductivity is found to be lower. The 0.4 h addition is a detailed rule formulated with careful consideration of large furnace charges and differences in temperature rise and average temperature characteristics of small samples.

(Example 42)
<Step 2: High temperature solid solution after normal horizontal continuous casting>
The temperature of the holding furnace is controlled at 1250° C., and the crystallizer adopts a conventional copper inner wall steel sleeve water-cooling crystallizer with only one cooling device. The cooling water flow rate is 50 L/min as conventional parameters, and the traction speed is 10 mm/sec. Copper alloy bars are obtained by casting. A copper alloy rod manufactured by horizontal continuous casting is solution treated. The solution treatment temperature was 900° C., the heating mode was online induction heating, and the treatment time was 40 minutes. The quenching adopts the conventional small-hole thermal spraying, setting 90 nozzles, setting the nozzle interval to 30 mm, the distance between the nozzle and the surface of the blank material to 60 mm, and the water pressure to 0.3 MPa.

Other steps and parameters are the same as in Example 25.
By comparing Examples 25 and 42, the horizontal continuous casting of the present invention significantly improves both hardness and electrical conductivity compared to conventional horizontal continuous casting and hot solid solution, and is an energy-consuming hot solid solution process. It turns out that you don't need

Table 3 Product Performance and Example Yield Summary

Claims (5)

A method for continuous extrusion of a copper alloy, comprising:
(1.1) The extrusion die uses a forged nickel-base alloy, which contains 0.05% C, 15% Cr, 6% Mo, 5% W, 2% Ti, The alloy containing 5.5% Al, balance Ni, is melted by vacuum smelting and electroslag remelting, and further homogenized before hot forging and heat treatment forming;
(1.2) Before extrusion, the extrusion die is first preheated to 500-600°C, and the copper alloy ingot is rapidly preheated to 700-750°C, then put into the die cavity and continuously extruded to form a blank. obtaining the material, wherein the rotation speed of the extrusion wheel is controlled to 3-8 rpm, the extrusion ratio is 3-8, and the extrusion gap is 0.6-2 mm;
(1.3) The blank material obtained in step (1.2) is subjected to high-intensity cooling water spray at the exit of the extrusion die, the spray device uses spray nozzles, and the nozzle spacing is 10-20 mm. Furthermore, the number of nozzles is provided according to the dimensions of the blank material, the distance between the nozzle and the surface of the blank material is 10 to 50 mm, the water pressure is 0.5 to 0.8 Mpa, and the blank material is heated from high temperature to room temperature. preventing precipitation decomposition of the supersaturated solid solution by quenching;
A method for continuous extrusion of a copper alloy having The forging of the nickel- based alloy is performed by first obtaining a smelted alloy ingot by melting by a vacuum smelting method and an electroslag remelting method, and then melting the smelted alloy ingot at 1250 ° C. After homogenization, it is formed by isothermal forging at 1000°C to 1050°C, and the amount of deformation is 80% to 90%. and then tempering at 300° C.-400° C. for 1-2 hours.
The method for continuously extruding a copper alloy according to claim 1, characterized in that: The copper alloy ingot is a copper alloy ingot in which all alloy elements in the ingot are in a supersaturated solid solution.
The continuous extrusion method for a copper alloy according to claim 1 or 2, characterized in that: A mold material used in the continuous extrusion method for a copper alloy according to any one of claims 1 to 3,
A nickel- based alloy comprising 0.05% C, 15% Cr, 6% Mo, 5% W, 2% Ti, 5.5% Al, balance Ni. including
A mold material used in a method for continuously extruding a copper alloy, characterized by: Use of the copper alloy continuous extrusion method according to claim 1 in copper alloy production.

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