CN111761257B - Preparation method and application of Cu-Mn-Ni-Si copper-based brazing filler metal - Google Patents
Preparation method and application of Cu-Mn-Ni-Si copper-based brazing filler metal Download PDFInfo
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- CN111761257B CN111761257B CN202010499728.9A CN202010499728A CN111761257B CN 111761257 B CN111761257 B CN 111761257B CN 202010499728 A CN202010499728 A CN 202010499728A CN 111761257 B CN111761257 B CN 111761257B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
A preparation method of Cu-Mn-Ni-Si copper-based solder comprises the following steps: the first step is as follows: proportioning each alloy element, and selecting and weighing corresponding raw materials; the second step is that: putting the raw materials into a medium-frequency induction melting furnace, and heating and melting; the third step: the raw materials are completely melted uniformly, and are injected into an online semi-solid treatment device through a launder for semi-solid treatment after degassing and deslagging; after the semi-solid treatment is finished, continuously introducing the steel wire into an upward continuous casting furnace, refining and then performing upward continuous casting to obtain a copper rod blank with the diameter of phi 10-30 mm; the fourth step: and (3) rolling the copper rod blank for multiple times, and repeatedly annealing at high temperature in the middle to finally obtain an alloy wire material with phi of 0.5-2.0 mm or a flat strip material with the thickness of 0.05-0.5 mm. The invention applies the up-drawing continuous casting technology and the continuous rolling technology to develop the Cu-Mn-Ni-Si strip solder and the wire solder. The stainless steel core plate is an ideal import substitute material, and realizes the localization of the solder for the hot air copper brazing of the stainless steel core plate.
Description
Technical Field
The invention belongs to the technical field of welding material preparation, relates to a continuous casting technology of up-drawing of a Cu-Mn-Ni-Si material rod blank and a continuous rolling technology of a strip material and a wire material, and particularly relates to a preparation method and application of a Cu-Mn-Ni-Si copper-based brazing filler metal.
Background
The melting point of Cu is 1083 ℃, the Cu can be directly used as a solder for soldering low-carbon steel, low-alloy steel, tungsten, molybdenum, nickel alloy, kovar alloy and the like under the reducing atmosphere and vacuum conditions, and the soldering temperature is 1100-1150 ℃. However, pure copper as a solder has the disadvantages of high melting point, poor corrosion resistance and oxidation resistance, and easily causes excessive growth of crystal grains of some soldered metals or alloys, resulting in deterioration of mechanical properties. By adding P, Zn, Ge, Sn, Ni, Mn, Ag, Co and other elements into Cu, some defects of pure Cu as solder can be overcome, and the physical property, the mechanical property and the weldability of the Cu solder are improved.
The copper-based brazing filler metal mainly comprises high copper alloy, copper-zinc alloy, copper-phosphorus alloy and special copper alloy, the high copper alloy brazing filler metal has good wettability and joint filling capacity on steel, can be used for directly brazing tungsten, molybdenum, iron, nickel and alloys thereof in reducing atmosphere or vacuum, and has higher brazing temperature; the copper-zinc alloy brazing filler metal is mainly used for brazing copper, copper alloy, nickel, steel, hard alloy and the like by methods of gas flame, induction, salt bath dipping and the like, when the Zn solder is less than 40%, the alloy strength and plasticity are excellent, but the solder Zn volatilizes and is not suitable for gas shielded brazing and vacuum brazing. The copper-phosphorus alloy metal air self-fluxing medium has wide application range, and P can reduce the melting point of Cu solder, so that the copper-phosphorus alloy metal air self-fluxing medium is suitable for soldering of various carbon steels. Other special copper alloy brazing filler metals such as CuPdNiMn and the like have excellent high-temperature performance, good weldability to steel and nickel alloy, low vapor pressure of palladium, difficult volatilization and suitability for gas shielded brazing and vacuum brazing, but Pd is a noble metal and is only used for special purposes. Cu-Mn also belongs to special copper alloy solders, but Cu-Mn binary solders are rare, and Ni or Co is usually added into the Cu-Mn alloy to improve the strength of the solder, but the melting point is increased.
The stainless steel core plate is an epoch-making new material, can be used for covering houses, and can be used for building bridges, paving roads, building vehicles, building airplanes, even vacuum covers outside super high-speed rails, and will bring subversive changes to the fields of buildings, roads, bridges, vehicles and aviation in the future. The stainless steel core plate is made of SUS304 stainless steel, is a particularly ' stiff material, is 10 times lighter than a ' reinforced concrete brother ' with the same size, and has a long service life. The stainless steel core plate is formed by two SUS304 stainless steel plates with a thin-wall core pipe, is welded by a hot air copper brazing technology, is heat-insulated and sound-insulated by filling rock wool in gaps, can be directly used as columns, beams and floor plates of buildings, and can be cut into the stainless steel core plate according to the design of the buildings. The corrosion resistance of the stainless steel core plate is not less than 100 times that of carbon steel, the service life of the stainless steel core plate is almost infinitely long, and the fire resistance of the stainless steel core plate is 300 times higher than that of a steel structure. The house can be built by three layers in one day and can be recovered by 100 percent without leaving any construction waste. In a word, the stainless steel core plate has many advantages, the steel structure cost is lowered subversively, and the future application is very considerable. At present, the stainless steel core plate is welded by using a hot air copper brazing technology, and the welding quality requirement is high, so that all welding materials are imported materials, and the cost is high.
In addition, Cu-Mn-Ni-Si alloy materials are currently used relatively rarely as copper-based brazing materials, typically wire, sheet and strip. The traditional method in industrial production is the repeated production of a single preparation induction smelting furnace, and has the problems of laggard process, poor consistency of components and other properties, incapability of realizing batch continuous production, low preparation efficiency, higher cost and the like. Further, the conventional manufacturing method mainly has the following disadvantages: 1. the raw material preparation adopts common discontinuous casting, the production efficiency is low, and the material utilization rate is low; 2. the round bar blank is obtained by a hot extrusion process, and the mechanical property and the metallographic structure consistency of the manufactured section are poor due to the uneven deformation in the hot extrusion process, so that the energy consumption in the production process is high; the surface quality of the round bar blank after hot extrusion is unstable, the defects of surface inclusion, peeling, extrusion embossing and the like are more, the treatment process is complex, and the product quality is influenced; 3. the continuous production can not be realized, the process is complex and the cost is high.
With the expansion of the market, higher requirements are put forward on the process and technology of materials, and a new technology capable of realizing batch continuous production, diversification and low cost needs to be developed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a Cu-Mn-Ni-Si copper-based brazing filler metal. According to the invention, a proper amount of Ni is added into the Cu-Mn alloy, and a proper amount of Si is further added, so that the melting point of the solder can be reduced, the wettability is improved, and the Cu-Mn alloy can be applied to soldering steel, high-temperature alloy, hard alloy and the like. The invention applies the up-drawing continuous casting technology and the continuous rolling technology to develop the Cu-Mn-Ni-Si strip solder and the wire solder. The stainless steel core plate is an ideal import substitute material, and realizes the localization of the solder for the hot air copper brazing of the stainless steel core plate.
In order to realize the purpose, the invention provides a preparation method of a Cu-Mn-Ni-Si copper-based brazing filler metal, which comprises the following chemical components in percentage by weight: mn: 23% -25%, Ni: 9-11%, Si 1.5-3%, Cu: the balance; the manufacturing method of the Cu-Mn-Ni-Si copper-based brazing filler metal comprises the following steps:
the first step is as follows: according to the component requirements of the alloy material, Mn: 23% -25%, Ni: 9-11%, Si 1.5-3%, Cu: the balance, proportioning each alloy element, selecting and weighing corresponding raw materials;
the second step is that: putting the raw materials into a medium-frequency induction melting furnace, and heating and melting; the smelting furnace adopts a graphite crucible with the pH value of 10-12, copper is firstly divided into three parts with the same quantity during smelting, and one part of the copper is laid at the bottom of the graphite crucible in the smelting furnace; then sequentially adding Ni and Si; then continuing to add the remaining two parts of copper; finally, Mn is added, and the raw materials in the graphite crucible are kept compact; then closing the vacuum chamber and vacuumizing, and preheating when the vacuum degree in the vacuum chamber reaches 10-13 Pa; then, the power is supplied to raise the temperature, and the melting power is increased, so that the raw materials are quickly melted; after the raw materials are melted, continuously heating, heating the metal liquid to 1460-1480 ℃, then preserving the heat for 5-10 min, and stirring the metal liquid to fully melt the metal liquid; meanwhile, after the molten metal is melted, argon is introduced into the furnace through a gas diffusion device at the bottom of the hearth; then closing a power supply of the medium-frequency induction furnace, continuing to ventilate, reducing the temperature of the molten metal to 1300-1320 ℃, preserving the temperature, continuing to introduce argon, and stirring the molten metal; wherein Mn adopts electrolytic manganese, Ni adopts electrolytic nickel, and Si adopts industrial silicon;
the third step: the raw materials are completely melted uniformly, and are injected into an online semi-solid treatment device through a launder for semi-solid treatment after degassing and deslagging; after the semi-solid treatment is finished, continuously introducing the steel bar into an upward continuous casting furnace, refining, performing upward continuous casting to obtain a copper bar blank with the diameter of 10-30 mm, wherein the upward continuous casting speed is 220-240 mm/min, performing online continuous solid solution strengthening for 2.5-3 hours at 980-990 ℃, and then cooling to room temperature by water cooling; the device for on-line continuous solid solution strengthening comprises a cylindrical body, wherein a heating device is arranged on the inside of the cylindrical body, a rotating device is arranged on the axis of the cylindrical body, a feeding hole and a discharging hole are respectively formed in the upper part and the lower part of the cylindrical body, and an argon inlet and a pressure control device are also arranged on the upper part of the cylindrical body; the whole process is carried out under the protective atmosphere of argon;
the fourth step: and (3) rolling the copper rod blank for multiple times, repeatedly annealing at high temperature in the middle, keeping the annealing temperature at 500-700 ℃ for 2-4 hours, and finally obtaining an alloy wire with the diameter of 0.5-2.0 mm or a flat strip with the thickness of 0.05-0.5 mm.
Preferably, in the second step, the medium-frequency induction smelting furnace adopts a medium-frequency induction electric furnace with the frequency of 5000-10000 Hz, two phases or three phases are adopted for supplying power, the power is 30-40 kW, and the whole stirring in the furnace is realized.
In any of the above schemes, preferably, in the third step, the device used for water-cooling includes a cooling cylinder body, the upper part and the lower part of the cooling cylinder body are respectively provided with a water outlet and a water inlet, the outside of the cooling cylinder body is provided with a water-cooling circulation device, the water-cooling circulation device is respectively connected with the water outlet and the water inlet through a pipeline, the inside of the cooling cylinder body is provided with an upper uniform water distribution disc and a lower uniform water distribution disc, the upper uniform water distribution disc and the lower uniform water distribution disc are positioned between the water outlet and the water inlet, and a cooling rotation device is arranged between the upper uniform water distribution disc and the lower uniform water distribution disc; the cooling cylinder body is provided with a feed hole and a discharge hole, the feed hole and the discharge hole are located between the upper uniform water distribution disc and the lower uniform water distribution disc, and the feed hole is located above the discharge hole.
In any one of the above aspects, preferably, in the fourth step, when the multi-pass rolling is performed, the rolling mill is used, the copper bar stock is clamped by the holding mechanism on the first lifting device of the rolling mill, and the copper bar stock is fed between the upper and lower rolls of the rolling mill by the push plate on the first lifting device of the rolling mill to be primarily rolled; the rolled copper rod blank enters a second lifting device of the rolling mill, and the copper rod blank after primary rolling is clamped by a holding mechanism on the second lifting device; the second lifting device descends, and the push plate on the second lifting device sends the copper rod blank subjected to primary rolling into the space between the upper roller and the lower roller for reverse secondary rolling; the copper rod blank after secondary rolling enters a first lifting device of a rolling mill and is clamped by a holding mechanism on the first lifting device; the first lifting device of the rolling mill descends, and the primary rolling step is repeated for three times of rolling; the rolled copper rod blank enters a second lifting device and is clamped by a holding mechanism on the second lifting device; and the second lifting device descends, the secondary rolling step is repeated for four times of rolling, and the like.
In any of the above embodiments, preferably, in the fourth step, the copper rod blank is subjected to multiple passes of heating, cold rolling and repeated intermediate annealing to obtain a flat strip or wire, wherein the number of passes may be 2 to 6.
In any one of the above embodiments, preferably, in the fourth step, the total deformation amount of the multi-pass rolling is 73 to 78%, and the deformation amount of the primary rolling is 40 to 45%.
In addition, in order to achieve the purpose, the invention also provides application of the Cu-Mn-Ni-Si copper-based brazing filler metal, and the Cu-Mn-Ni-Si alloy wire and strip materials with different specifications obtained in the steps are mainly applied to the hot air welding field of buildings, bridges, pavements, vehicle manufacturing, high-speed rail vacuum covers and aircraft stainless steel core plates.
The invention has the beneficial effects that:
1. according to the invention, a proper amount of Ni is added into the Cu-Mn alloy, and a proper amount of Si is further added, so that the melting point of the solder can be reduced, the wettability is improved, and the Cu-Mn alloy can be applied to soldering steel, high-temperature alloy, hard alloy and the like. The invention applies the up-drawing continuous casting technology and the continuous rolling technology to develop the Cu-Mn-Ni-Si strip solder and the wire solder. The stainless steel core plate is an ideal import substitute material, and the localization of the solder for the hot air copper brazing of the stainless steel core plate is realized.
2. The up-drawing continuous casting technology is used as a novel copper alloy wire rod and plate strip production technology, the produced wire blank material has uniform components, short process flow and stable product performance, and the continuous production of materials such as copper-magnesium alloy wire blanks, silver-copper alloy wire blanks and the like is successfully realized. On the basis, the Cu-Mn-Ni-Si alloy material is developed by applying the upward continuous casting technology, the process flow is shortened, the product performance is improved, and the processing and production process is further developed towards the energy-saving, material-saving and environment-friendly directions. Meanwhile, the combined continuous hot-rolling and cold-rolling technology is applied to realize the batch industrial production of Cu-Mn-Ni-Si alloy strips and wires.
3. The production process of the invention is environment-friendly and energy-saving, has good product consistency and controllable cost, has great propulsion effect on the hot air welding production of the stainless steel core plate, accelerates the application of the stainless steel core plate in various fields such as houses, bridge building, paving, vehicle building, airplane building, even vacuum covers outside super high-speed rails and the like, and brings subversive revolution to the fields of buildings, roads and bridges, vehicles and aviation in the future.
4. The invention introduces the up-drawing continuous casting technology, breaks through the traditional preparation problem of the Cu-Mn-Ni-Si multi-element alloy material, obtains Cu-Mn-Ni-Si alloy up-drawing copper rods with different components and specifications, realizes continuous production, improves the production efficiency and improves the material utilization rate; obtaining a Cu-Mn-Ni-Si alloy round rod blank by an upward continuous casting technology, and further realizing the continuous production of Cu-Mn-Ni-Si alloy strips and wire rods by continuous hot and cold rolling technologies; the wire and strip prepared by the method have smooth and bright surfaces, consistent performance and structure, stable quality and less energy consumption in the production process.
Detailed Description
The technical solutions of the present application will be described in detail below with reference to specific embodiments of the present application, but the following examples are only for understanding the present invention, and the examples and features of the examples in the present application can be combined with each other, and the present application can be implemented in various different ways as defined and covered by the claims.
Example 1
A preparation method of Cu-Mn-Ni-Si copper-based solder comprises the following chemical components in percentage by weight: mn: 23%, Ni: 11%, Si:1.5, Cu: the balance; the manufacturing method of the Cu-Mn-Ni-Si copper-based brazing filler metal comprises the following steps:
the first step is as follows: according to the component requirements of the alloy material, Mn: 23%, Ni: 11%, Si:1.5, Cu: the balance, proportioning each alloy element, selecting and weighing corresponding raw materials;
the second step is that: putting the raw materials into a medium-frequency induction melting furnace, and heating and melting; the smelting furnace adopts a graphite crucible with the pH value of 12, copper is firstly divided into three parts with the same quantity when smelting, and one part of the copper is laid at the bottom of the graphite crucible in the smelting furnace; then sequentially adding Ni and Si; then continuing to add the remaining two parts of copper; finally, Mn is added, and the raw materials in the graphite crucible are kept compact; then closing the vacuum chamber and vacuumizing, and preheating when the vacuum degree in the vacuum chamber reaches 10 Pa; then power is supplied to raise the temperature, and the melting power is increased, so that the raw materials are quickly melted; after the melting of the raw materials is finished, continuing heating, heating the metal liquid to 1480 ℃, then preserving the temperature for 5min, and stirring the metal liquid to fully melt the metal liquid; meanwhile, after the molten metal is melted, argon is introduced into the furnace through a gas diffusion device at the bottom of the hearth; then closing a power supply of the medium-frequency induction furnace, continuing to ventilate, reducing the temperature of the molten metal to 1320 ℃, keeping the temperature, continuing to introduce argon, and stirring the molten metal; wherein Mn adopts electrolytic manganese, Ni adopts electrolytic nickel, and Si adopts industrial silicon;
the third step: the raw materials are completely melted uniformly, and are injected into an online semi-solid treatment device through a launder for semi-solid treatment after degassing and deslagging; after the semi-solid treatment is finished, continuously introducing the steel bar into an upward continuous casting furnace, refining and then performing upward continuous casting to obtain a copper bar blank with the diameter of phi 10mm, wherein the upward continuous casting speed is 240mm/min, then performing online continuous solid solution strengthening for 2.5 hours at 980 ℃, and then performing water cooling to room temperature; the device for on-line continuous solid solution strengthening comprises a cylindrical body, wherein a heating device is arranged on the inside of the cylindrical body, a rotating device is arranged on the axis of the cylindrical body, a feeding hole and a discharging hole are respectively formed in the upper part and the lower part of the cylindrical body, and an argon inlet and a pressure control device are also arranged on the upper part of the cylindrical body; the whole process is carried out under the protective atmosphere of argon;
the fourth step: and (3) rolling the copper rod blank for multiple times, repeatedly annealing at high temperature in the middle, keeping the annealing temperature at 700 ℃ for 2 hours, and finally obtaining the alloy wire with the diameter of 2.0mm or the flat strip with the thickness of 0.05 mm.
In the second step, the medium-frequency induction smelting furnace adopts a medium-frequency induction electric furnace with the frequency of 10000Hz, adopts two-phase or three-phase power supply, has the power of 30kW, and realizes integral stirring in the furnace.
In the third step, the device used for water cooling comprises a cooling cylinder body, the upper part and the lower part of the cooling cylinder body are respectively provided with a water outlet hole and a water inlet hole, the outside of the cooling cylinder body is provided with a water cooling circulation device, the water cooling circulation device is respectively connected with the water outlet hole and the water inlet hole through pipelines, the inside of the cooling cylinder body is provided with an upper uniform water distribution disc and a lower uniform water distribution disc, the upper uniform water distribution disc and the lower uniform water distribution disc are positioned between the water outlet hole and the water inlet hole, and a cooling rotating device is arranged between the upper uniform water distribution disc and the lower uniform water distribution disc; the cooling cylinder body is provided with a feed hole and a discharge hole, the feed hole and the discharge hole are located between the upper uniform water distribution disc and the lower uniform water distribution disc, and the feed hole is located above the discharge hole.
In the fourth step, a rolling mill is adopted when multi-pass rolling is carried out, a holding mechanism on a first lifting device of the rolling mill is used for clamping the copper rod blank, and a push plate on the first lifting device of the rolling mill is used for sending the copper rod blank into a space between an upper roller and a lower roller of the rolling mill for primary rolling; the rolled copper rod blank enters a second lifting device of the rolling mill, and the copper rod blank after primary rolling is clamped by a holding mechanism on the second lifting device; the second lifting device descends, and the push plate on the second lifting device sends the copper rod blank subjected to primary rolling into the space between the upper roller and the lower roller for reverse secondary rolling; the copper rod blank after secondary rolling enters a first lifting device of a rolling mill and is clamped by a holding mechanism on the first lifting device; the first lifting device of the rolling mill descends, and the primary rolling step is repeated for three times of rolling; the rolled copper rod blank enters a second lifting device and is clamped by a holding mechanism on the second lifting device; and the second lifting device descends, the secondary rolling step is repeated for four times of rolling, and the like.
In the fourth step, the copper rod blank is subjected to multi-pass hot rolling, cold rolling and repeated intermediate annealing to obtain a flat strip or wire, wherein the number of passes can be 6.
In the fourth step, the total deformation of the multi-pass rolling is 73%, and the deformation of the primary rolling is 45%.
In addition, the application of the Cu-Mn-Ni-Si copper-based brazing filler metal is that the Cu-Mn-Ni-Si alloy wire and strip materials with different specifications obtained in the steps are mainly applied to the hot air welding field of buildings, bridge construction, road paving, vehicle manufacturing, high-speed rail vacuum covers and airplane stainless steel core plates.
Example 2
A preparation method of Cu-Mn-Ni-Si copper-based solder comprises the following chemical components in percentage by weight: mn: 25%, Ni: 9%, Si: 3%, Cu: the balance; the manufacturing method of the Cu-Mn-Ni-Si copper-based brazing filler metal comprises the following steps:
the first step is as follows: according to the component requirements of the alloy material, Mn: 25%, Ni: 9%, Si: 3%, Cu: the balance, proportioning each alloy element, selecting and weighing corresponding raw materials;
the second step is that: putting the raw materials into a medium-frequency induction melting furnace, and heating and melting; the smelting furnace adopts a graphite crucible with the pH value of 10, copper is firstly divided into three parts with the same quantity during smelting, and one part of the copper is laid at the bottom of the graphite crucible in the smelting furnace; then sequentially adding Ni and Si; then continuing to add the remaining two parts of copper; finally, Mn is added, and the raw materials in the graphite crucible are kept compact; then closing the vacuum chamber and vacuumizing, and preheating when the vacuum degree in the vacuum chamber reaches 13 Pa; then, the power is supplied to raise the temperature, and the melting power is increased, so that the raw materials are quickly melted; after the melting of the raw materials is finished, continuously heating, heating the metal liquid to 1460 ℃, then preserving the temperature for 10min, and stirring the metal liquid to fully melt the metal liquid; meanwhile, after the molten metal is melted, argon is introduced into the furnace through a gas diffusion device at the bottom of the hearth; then closing a power supply of the medium-frequency induction furnace, continuing to ventilate, reducing the temperature of the molten metal to 1300 ℃, keeping the temperature, continuing to introduce argon, and stirring the molten metal; wherein Mn adopts electrolytic manganese, Ni adopts electrolytic nickel, and Si adopts industrial silicon; the industrial silicon is prepared by the following steps: crushing and finely grinding the industrial silicon block, screening to obtain 100-300-mesh powder, washing with water at room temperature, and drying to obtain silicon powder; pretreating silicon powder, cleaning after the pretreatment is finished, filtering, separating and drying to obtain porous silicon powder; annealing the porous silicon powder, heating to the annealing temperature of 700-800 ℃ at the annealing furnace heating rate of 8-10 ℃/min under the annealing atmosphere with the introduction flow of 100-200 ml/min, annealing for 5-6 h, and cooling to the room temperature after the annealing is finished; carrying out boric acid cleaning treatment on porous silicon powder, wherein the liquid-solid ratio is more than 6:1mL/g, and stirring and leaching for 30-40 min at the temperature of 20-30 ℃; and filtering, washing and drying after leaching. The pretreatment comprises the following steps: and placing the silicon powder into a mixed solution at the temperature of 20-30 ℃ and the liquid-solid ratio of 6:1mL/g for etching for 50-60 min, wherein the mixed solution is hydrogen peroxide and the concentration of the hydrogen peroxide is 1-2 mol/L. The preparation process can effectively reduce the content of impurities in the industrial silicon, is simple to operate and high in practicability, and cannot improve the cost of the prior art.
The third step: the raw materials are completely melted uniformly, and are injected into an online semi-solid treatment device through a launder for semi-solid treatment after degassing and deslagging; after the semi-solid treatment is finished, continuously introducing the steel bar into an upward continuous casting furnace, refining and then performing upward continuous casting to obtain a copper bar blank with the diameter of phi 30mm, wherein the upward continuous casting speed is 220mm/min, then performing online continuous solid solution strengthening at 990 ℃ for 3 hours, and then performing water cooling to room temperature; the device for on-line continuous solid solution strengthening comprises a cylindrical body, wherein a heating device is arranged on the inside of the cylindrical body, a rotating device is arranged on the axis of the cylindrical body, a feed hole and a discharge hole are respectively formed in the upper part and the lower part of the cylindrical body, and an argon inlet and a pressure control device are also arranged on the upper part of the cylindrical body; the whole process is carried out under the protective atmosphere of argon;
the fourth step: and (3) rolling the copper rod blank for multiple times, repeatedly annealing at high temperature in the middle, keeping the annealing temperature at 500 ℃ for 4 hours, and finally obtaining the alloy wire with the diameter of 0.5mm or the flat strip with the thickness of 0.5 mm.
In the second step, the medium-frequency induction smelting furnace adopts a medium-frequency induction electric furnace with the frequency of 5000Hz, adopts two-phase or three-phase power supply, and realizes the integral stirring in the furnace, wherein the power is 40 kW.
In the third step, the device adopted by the water cooling comprises a cooling cylinder body, the upper part and the lower part of the cooling cylinder body are respectively provided with a water outlet hole and a water inlet hole, the outside of the cooling cylinder body is provided with a water cooling circulation device, the water cooling circulation device is respectively connected with the water outlet hole and the water inlet hole through pipelines, the inside of the cooling cylinder body is provided with an upper uniform water distribution disc and a lower uniform water distribution disc, the upper uniform water distribution disc and the lower uniform water distribution disc are positioned between the water outlet hole and the water inlet hole, and a cooling rotating device is arranged between the upper uniform water distribution disc and the lower uniform water distribution disc; the cooling cylinder body is provided with a feed hole and a discharge hole, the feed hole and the discharge hole are located between the upper uniform water distribution disc and the lower uniform water distribution disc, and the feed hole is located above the discharge hole.
In the fourth step, a rolling mill is adopted when multi-pass rolling is carried out, a holding mechanism on a first lifting device of the rolling mill is used for clamping the copper rod blank, and a push plate on the first lifting device of the rolling mill is used for sending the copper rod blank into a space between an upper roller and a lower roller of the rolling mill for primary rolling; the rolled copper rod blank enters a second lifting device of the rolling mill, and the copper rod blank after primary rolling is clamped by a holding mechanism on the second lifting device; the second lifting device descends, and the push plate on the second lifting device sends the copper rod blank subjected to primary rolling into the space between the upper roller and the lower roller for reverse secondary rolling; the copper rod blank after the secondary rolling enters a first lifting device of the rolling mill and is clamped by a holding mechanism on the first lifting device; the first lifting device of the rolling mill descends, and the primary rolling step is repeated for three times of rolling; the rolled copper rod blank enters a second lifting device and is clamped by a holding mechanism on the second lifting device; and the second lifting device descends, the secondary rolling step is repeated for four times of rolling, and the like.
In the fourth step, the copper rod blank is subjected to multi-pass heating, cold rolling and repeated intermediate annealing to obtain a flat strip or wire, wherein the pass can be 2 times.
In the fourth step, the total deformation of the multi-pass rolling is 78%, and the deformation of the primary rolling is 40%.
In addition, the application of the Cu-Mn-Ni-Si copper-based brazing filler metal is that the Cu-Mn-Ni-Si alloy wire and strip materials with different specifications obtained in the steps are mainly applied to the hot air welding field of buildings, bridge construction, road paving, vehicle manufacturing, high-speed rail vacuum covers and airplane stainless steel core plates.
Example 3
A preparation method of Cu-Mn-Ni-Si copper-based solder comprises the following chemical components in percentage by weight: mn: 24%, Ni: 10%, Si: 2%, Cu: the balance; the manufacturing method of the Cu-Mn-Ni-Si copper-based brazing filler metal comprises the following steps:
the first step is as follows: according to the component requirements of the alloy material, Mn: 24%, Ni: 10%, Si: 2%, Cu: the balance, proportioning each alloy element, selecting and weighing corresponding raw materials;
the second step: putting the raw materials into a medium-frequency induction melting furnace, and heating and melting; the smelting furnace adopts a graphite crucible with the pH value of 11, copper is firstly divided into three parts with the same quantity when smelting, and one part of the copper is laid at the bottom of the graphite crucible in the smelting furnace; then sequentially adding Ni and Si; then continuing to add the remaining two parts of copper; finally, adding Mn, and keeping the raw materials in the graphite crucible compact; then closing the vacuum chamber and vacuumizing, and preheating when the vacuum degree in the vacuum chamber reaches 12 Pa; then, the power is supplied to raise the temperature, and the melting power is increased, so that the raw materials are quickly melted; after the melting of the raw materials is finished, continuously heating, heating the metal liquid to 1470 ℃, then preserving the temperature for 8min, and stirring the metal liquid to fully melt the metal liquid; meanwhile, after the molten metal is melted, argon is introduced into the furnace through a gas diffusion device at the bottom of the hearth; then closing a power supply of the medium-frequency induction furnace, continuing to ventilate, reducing the temperature of the molten metal to 1310 ℃, preserving the temperature, continuing to introduce argon, and stirring the molten metal; wherein Mn adopts electrolytic manganese, Ni adopts electrolytic nickel, and Si adopts industrial silicon; the nickel electrolysis comprises the following steps: (1) adding the electrolyte subjected to chemical impurity removal into an electrolytic cell, and starting circulating filtration and heating; (2) adding an electrolytic nickel raw material to be plated into a roller, wherein the roller is connected with a circuit cathode, and an electrolytic bath anode is connected with a circuit anode; the roller is obliquely arranged in the electrolytic bath, and the motor is connected with the roller; (3) controlling the voltage interval of the electrolytic bath to be 2-3V, and gradually increasing the voltage along with the lengthening of the growth time of the electrolytic nickel raw material after keeping for 26-30 hours, wherein the voltage interval is 10-12V. The electrolytic nickel raw material is sulfur-containing electrolytic nickel, and the sulfur content of the sulfur-containing electrolytic nickel is controlled to be 0.02-0.03%. The electrolyte used was: a nickel sulfamate system electrolytic solution comprising nickel sulfamate: 300-400g/L, nickel chloride: 10-15g/L, orthoboric acid: 30-35 g/L. Regulating pH value of the solution to 3-4 with sulfamic acid or nickel carbonate at 45-50 deg.c. The process for electrolyzing nickel reduces a large amount of labor hour and realizes continuous production. The electrolytic nickel material with different shapes which is suitable for the requirements of users can be produced according to the requirements of customers.
The third step: the raw materials are completely melted uniformly, and are injected into an online semi-solid treatment device through a launder for semi-solid treatment after degassing and deslagging; after the semi-solid treatment is finished, continuously introducing the steel into an upward continuous casting furnace, refining and then performing upward continuous casting to obtain a copper rod blank with the diameter of phi 20mm, wherein the upward continuous casting speed is 230mm/min, then performing online continuous solid solution strengthening at 985 ℃ for 2.8 hours, and then performing water cooling to room temperature; the device for on-line continuous solid solution strengthening comprises a cylindrical body, wherein a heating device is arranged on the inside of the cylindrical body, a rotating device is arranged on the axis of the cylindrical body, a feeding hole and a discharging hole are respectively formed in the upper part and the lower part of the cylindrical body, and an argon inlet and a pressure control device are also arranged on the upper part of the cylindrical body; the whole process is carried out under the protective atmosphere of argon;
the fourth step: and (3) rolling the copper rod blank for multiple times, repeatedly annealing at high temperature in the middle, keeping the annealing temperature at 600 ℃ for 3 hours, and finally obtaining the alloy wire with the diameter of 1mm or the flat strip with the thickness of 0.25 mm.
In the second step, the medium-frequency induction smelting furnace adopts a medium-frequency induction electric furnace with the frequency of 8000Hz, adopts two-phase or three-phase power supply, has the power of 35kW, and realizes integral stirring in the furnace.
In the third step, the device used for water cooling comprises a cooling cylinder body, the upper part and the lower part of the cooling cylinder body are respectively provided with a water outlet hole and a water inlet hole, the outside of the cooling cylinder body is provided with a water cooling circulation device, the water cooling circulation device is respectively connected with the water outlet hole and the water inlet hole through pipelines, the inside of the cooling cylinder body is provided with an upper uniform water distribution disc and a lower uniform water distribution disc, the upper uniform water distribution disc and the lower uniform water distribution disc are positioned between the water outlet hole and the water inlet hole, and a cooling rotating device is arranged between the upper uniform water distribution disc and the lower uniform water distribution disc; the cooling cylinder body is provided with a feed hole and a discharge hole, the feed hole and the discharge hole are located between the upper uniform water distribution disc and the lower uniform water distribution disc, and the feed hole is located above the discharge hole.
In the fourth step, a rolling mill is adopted when multi-pass rolling is carried out, a holding mechanism on a first lifting device of the rolling mill is used for clamping the copper rod blank, and a push plate on the first lifting device of the rolling mill is used for sending the copper rod blank into a space between an upper roller and a lower roller of the rolling mill for primary rolling; the rolled copper rod blank enters a second lifting device of the rolling mill, and the copper rod blank after primary rolling is clamped by a holding mechanism on the second lifting device; the second lifting device descends, and the push plate on the second lifting device sends the copper rod blank subjected to primary rolling into the space between the upper roller and the lower roller for reverse secondary rolling; the copper rod blank after secondary rolling enters a first lifting device of a rolling mill and is clamped by a holding mechanism on the first lifting device; the first lifting device of the rolling mill descends, and the primary rolling step is repeated for three times of rolling; the rolled copper rod blank enters a second lifting device and is clamped by a holding mechanism on the second lifting device; and the second lifting device descends, the secondary rolling step is repeated for four times of rolling, and the like.
In the fourth step, the copper rod blank is subjected to multi-pass heating, cold rolling and repeated intermediate annealing to obtain a flat strip or wire, wherein the pass can be 4 times.
In the fourth step, the total deformation of the multi-pass rolling is 75%, and the deformation of the primary rolling is 42%.
In addition, the application of the Cu-Mn-Ni-Si copper-based brazing filler metal is that the Cu-Mn-Ni-Si alloy wire and strip materials with different specifications obtained in the steps are mainly applied to the hot air welding field of buildings, bridge construction, road paving, vehicle manufacturing, high-speed rail vacuum covers and airplane stainless steel core plates.
Further, in order to achieve better technical effects, the technical solutions in the above embodiments may be combined arbitrarily to meet various requirements of practical applications.
Tests prove that the mechanical property of the copper-based brazing filler metal prepared by the embodiment reaches 98.5-99% IACS, and the tensile strength reaches 700-.
The above embodiments show that the addition of a proper amount of Ni and the further addition of a proper amount of Si to the Cu-Mn alloy can lower the melting point of the solder and improve the wettability, and can be applied to soldering steel, high-temperature alloy, hard alloy and the like. The invention applies the up-drawing continuous casting technology and the continuous rolling technology to develop the Cu-Mn-Ni-Si strip solder and the wire solder. The stainless steel core plate is an ideal import substitute material, and realizes the localization of the solder for the hot air copper brazing of the stainless steel core plate.
The up-drawing continuous casting technology is used as a novel copper alloy wire rod and plate strip production technology, the produced wire blank material has uniform components, short process flow and stable product performance, and the continuous production of materials such as copper-magnesium alloy wire blanks, silver-copper alloy wire blanks and the like is successfully realized. On the basis, the Cu-Mn-Ni-Si alloy material is developed by applying the upward continuous casting technology, the process flow is shortened, the product performance is improved, and the processing and production process is further developed towards the direction of energy conservation, material conservation and environmental protection. Meanwhile, the combined continuous hot-rolling and cold-rolling technology is applied to realize the batch industrial production of Cu-Mn-Ni-Si alloy strips and wires.
The production process of the invention is environment-friendly and energy-saving, has good product consistency and controllable cost, has great propulsion effect on the hot air welding production of the stainless steel core plate, accelerates the application of the stainless steel core plate in various fields such as houses, bridge building, paving, vehicle building, airplane building, even vacuum covers outside super high-speed rails and the like, and brings subversive revolution to the fields of buildings, roads and bridges, vehicles and aviation in the future.
The invention introduces the up-drawing continuous casting technology, breaks through the traditional preparation problem of the Cu-Mn-Ni-Si multi-element alloy material, obtains Cu-Mn-Ni-Si alloy up-drawing copper rods with different components and specifications, realizes continuous production, improves the production efficiency and improves the material utilization rate; obtaining a Cu-Mn-Ni-Si alloy round rod blank by an upward continuous casting technology, and further realizing the continuous production of Cu-Mn-Ni-Si alloy strips and wires by continuous hot rolling and cold rolling technologies; the wire and strip prepared by the method have smooth and bright surfaces, consistent performance and structure, stable quality and less energy consumption in the production process.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (4)
1. The preparation method of the Cu-Mn-Ni-Si copper-based brazing filler metal is characterized in that the Cu-Mn-Ni-Si copper-based brazing filler metal comprises the following chemical components in percentage by weight: mn: 23% -25%, Ni: 9-11%, Si 1.5-3%, Cu: the balance; the manufacturing method of the Cu-Mn-Ni-Si copper-based brazing filler metal comprises the following steps:
the first step is as follows: according to the component requirement of the alloy material, Mn: 23% -25%, Ni: 9-11%, Si 1.5-3%, Cu: the balance, proportioning each alloy element, selecting and weighing corresponding raw materials;
the second step is that: putting the raw materials into a medium-frequency induction melting furnace, and heating and melting; the smelting furnace adopts a graphite crucible with the pH value of 10-12, copper is firstly divided into three parts with the same quantity during smelting, and one part of the copper is laid at the bottom of the graphite crucible in the smelting furnace; then sequentially adding Ni and Si; then continuously adding the rest two parts of copper; finally, Mn is added, and the raw materials in the graphite crucible are kept compact; then closing the vacuum chamber and vacuumizing, and preheating when the vacuum degree in the vacuum chamber reaches 10-13 Pa; then, the power is supplied to raise the temperature, and the melting power is increased, so that the raw materials are quickly melted; after the raw materials are melted, continuously heating, heating the metal liquid to 1460-1480 ℃, then preserving the heat for 5-10 min, and stirring the metal liquid to fully melt the metal liquid; meanwhile, after the molten metal is melted, argon is introduced into the furnace through a gas diffusion device at the bottom of the hearth; then closing a power supply of the medium-frequency induction furnace, continuing to ventilate, reducing the temperature of the molten metal to 1300-1320 ℃, preserving the temperature, continuing to introduce argon, and stirring the molten metal; wherein Mn adopts electrolytic manganese, Ni adopts electrolytic nickel, and Si adopts industrial silicon;
in the second step, the medium-frequency induction smelting furnace adopts a medium-frequency induction electric furnace with the frequency of 5000-10000 Hz, two-phase or three-phase power supply is adopted, the power is 30-40 kW, and the whole stirring in the furnace is realized;
the third step: the raw materials are completely melted uniformly, and are injected into an online semi-solid treatment device through a launder for semi-solid treatment after degassing and deslagging; after the semi-solid treatment is finished, continuously introducing the steel bar into an upward continuous casting furnace, refining, performing upward continuous casting to obtain a copper bar blank with the diameter of 10-30 mm, wherein the upward continuous casting speed is 220-240 mm/min, performing online continuous solid solution strengthening for 2.5-3 hours at 980-990 ℃, and then cooling to room temperature by water cooling; the device for on-line continuous solid solution strengthening comprises a cylindrical body, wherein a heating device is arranged on the inside of the cylindrical body, a rotating device is arranged on the axis of the cylindrical body, a feed hole and a discharge hole are respectively formed in the upper part and the lower part of the cylindrical body, and an argon inlet and a pressure control device are also arranged on the upper part of the cylindrical body; the whole process of the steps is carried out under the protective atmosphere of argon;
in the third step, the device adopted by the water cooling comprises a cooling cylinder body, the upper part and the lower part of the cooling cylinder body are respectively provided with a water outlet hole and a water inlet hole, the outside of the cooling cylinder body is provided with a water cooling circulation device, the water cooling circulation device is respectively connected with the water outlet hole and the water inlet hole through pipelines, the inside of the cooling cylinder body is provided with an upper uniform water distribution disc and a lower uniform water distribution disc, the upper uniform water distribution disc and the lower uniform water distribution disc are positioned between the water outlet hole and the water inlet hole, and a cooling rotating device is arranged between the upper uniform water distribution disc and the lower uniform water distribution disc; the cooling cylinder body is provided with a feed hole and a discharge hole, the feed hole and the discharge hole are positioned between the upper uniform water distribution plate and the lower uniform water distribution plate, and the feed hole is positioned above the discharge hole;
the fourth step: carrying out multi-pass rolling on the copper rod blank, repeatedly annealing at high temperature in the middle, keeping the annealing temperature at 500-700 ℃ for 2-4 hours, and finally obtaining an alloy wire with phi of 0.5-2.0 mm or a flat strip with the thickness of 0.05-0.5 mm;
in the fourth step, a rolling mill is adopted when multi-pass rolling is carried out, a holding mechanism on a first lifting device of the rolling mill is used for clamping the copper rod blank, and a push plate on the first lifting device of the rolling mill is used for sending the copper rod blank into a space between an upper roller and a lower roller of the rolling mill for primary rolling; the rolled copper rod blank enters a second lifting device of the rolling mill, and the copper rod blank after primary rolling is clamped by a holding mechanism on the second lifting device; the second lifting device descends, and the push plate on the second lifting device sends the copper rod blank subjected to primary rolling into the space between the upper roller and the lower roller for reverse secondary rolling; the copper rod blank after secondary rolling enters a first lifting device of a rolling mill and is clamped by a holding mechanism on the first lifting device; the first lifting device of the rolling mill descends, and the primary rolling step is repeated for three times of rolling; the rolled copper rod blank enters a second lifting device and is clamped by a holding mechanism on the second lifting device; and the second lifting device descends, the secondary rolling step is repeated for four times of rolling, and the like.
2. The method for preparing the Cu-Mn-Ni-Si copper-based brazing filler metal according to claim 1, wherein in the fourth step, the copper rod blank is subjected to multi-pass heating, cold rolling and repeated intermediate annealing to obtain a flat strip or wire, wherein the number of passes can be 2-6.
3. The method for preparing a Cu-Mn-Ni-Si copper-based brazing filler metal according to claim 1, wherein in the fourth step, the total deformation amount of the multi-pass rolling is 73 to 78%, and the deformation amount of the first rolling is 40 to 45%.
4. Use of a Cu-Mn-Ni-Si copper-based brazing filler metal, characterized in that it is produced according to the method of any one of claims 1 to 3, and that the Cu-Mn-Ni-Si alloy wire and strip of different specifications obtained in the above steps are used for hot air welding of building, bridge construction, road paving, vehicle construction, high-speed rail vacuum hoods, aircraft stainless steel core panels.
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| CN113857250B (en) * | 2021-09-15 | 2024-04-09 | 昆明理工大学 | Method for preparing metal semi-solid slurry by multistage rolling-annealing SIMA method |
| CN113828961B (en) * | 2021-10-20 | 2022-09-23 | 宁波兴业盛泰集团有限公司 | Lead-free copper alloy solder and preparation method thereof |
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