CN103480987B - A kind of preparation method of high fragility copper zinc welding rod/weld tabs - Google Patents
A kind of preparation method of high fragility copper zinc welding rod/weld tabs Download PDFInfo
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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
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Abstract
The invention discloses a kind of preparation method of high fragility copper zinc welding rod/weld tabs, first pltine cylinder ingot is prepared, then composite ingot is formed by pltine ingot casting press-in pltine cylinder ingot, enter in electric furnace and after preheating, be squeezed into bar-shaped or banded alloy, after online annealing, rolling or be drawn into the solder of required diameter, then enters diffusion annealing in vacuum resistance furnace, can obtain satisfactory welding wire or weld tabs.The invention has the advantages that simple operation, good stability and cost is lower.Solve the problem that existing high fragility copper-zinc solder is difficult to be processed into welding wire, weld tabs, copper-zinc solder can be processed into the welding wire of diameter≤2.5mm or the weld tabs of thickness≤0.3mm by the inventive method, meets the requirement of soldering production technology.
Description
Technical field
The present invention relates to the preparation of solder, especially relate to a kind of preparation method of high fragility copper zinc welding rod/weld tabs.
Background technology
Solder is as the very important welding material of a class, be all essential, vital connecting material in the industries such as household electrical appliance, motor, electric appliance and electronic, building and ornament materials, weaponry, soldering tech plays important role in these industries.In order to pursue brazing manufacturability and Technical Economy, Solders Research person at continuous development of new low-silver solder and copper base solder, and constantly improves mobility and the wetting and spreading of solder.For copper-zinc solder, in order to reduce the fusing point of copper, researcher adds Zn content in former solder formula, and in solder, add tin, manganese, silver etc.But according to ormolu phase (see figure 1), along with the increase of zinc content, in alloy structure, can the phases such as α, β, γ be there is.Wherein α is the good solid solution phase of intensity and plasticity; β is that intensity is high, the Compound Phase that cold working plasticity is low; γ is extremely crisp Compound Phase.Therefore by increasing the processing characteristics that also can reduce solder while zinc reduces fusing point.
Existing copper-zinc solder zinc when soldering is easy to volatilization, and its result makes the fusing point of solder increase, and can produce pore in joint, destroys the compactness of solder.In addition, zinc fume is poisonous, is unfavorable for workers ' health again.In order to reduce the volatilization of zinc, can add a small amount of silicon in copper-zinc solder, silicon is oxidized when soldering, forms the silicate of low melting point, float over liquid solder surface, prevent the evaporation of zinc with the borate in brazing flux.But silicon significantly can reduce the solubility of zinc in copper, impel and generate β phase, solder is become fragile.In addition, though add the spreadability that tin etc. can improve solder in copper-zinc solder, the solubility of zinc in copper can be reduced equally, solder is become fragile, solder cannot be processed into welding wire, weld tabs, foil-shaped brazing material or powdered filler metal can only be made with rapid solidification method, limit its scope of application.Therefore, inventing a kind of preparation method being processed into the high fragility copper-zinc solder of welding wire or weld tabs, is technical problem urgently to be resolved hurrily in solder production process.
Summary of the invention
The object of the invention is to solve by 42 ~ 64% zinc, 0 ~ 2% tin, 0 ~ 0.5% silicon, the preparation method of the high fragility copper zinc welding rod/weld tabs of surplus copper composition.
For achieving the above object, the present invention can take following technical proposals:
The preparation method of high fragility copper zinc welding rod/weld tabs of the present invention, comprises the steps:
The first step, prepares the alloy cylinder ingot that percentage by weight is zinc 38 ~ 40, copper 60 ~ 62
Metallic copper is entered intermediate frequency furnace fusing, when temperature reaches 1100 ~ 1200 DEG C, add metallic zinc, fully cover by complex salt after fusion; The cylindrical shape ingot casting obtaining external diameter 95mm, height 355mm, endoporus 30 ~ 60mm is poured into a mould when molten metal temperature being reduced to 1050-1100 DEG C; Ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use;
Second step, prepares the alloy cast ingot that percentage by weight is zinc 64 ~ 80, copper 20 ~ 36
Metallic copper is entered intermediate frequency furnace fusing, when temperature reaches 1100 ~ 1200 DEG C, add metallic zinc, fully cover by complex salt after fusion; The cylindrical ingot obtaining external diameter 35 ~ 65mm, height 375mm is poured into a mould when molten metal temperature being reduced to 1050 ~ 1100 DEG C; Cylindrical ingot is entered 450 ~ 700 DEG C of annealing in resistance furnace and, after 3 ~ 8 hours, be processed into external diameter identical with cylinder ingot endoporus, the ingot casting of high 360mm;
3rd step, is axially pressed into ingot casting in the endoporus of cylinder ingot and forms composite ingot;
4th step, enters composite ingot in resistance furnace that 550 ~ 780 DEG C of preheatings are after 4 hours, and compound Isothermal Extrusion becomes bar-shaped or banded alloy; After online annealing, banded alloy rolling becomes the strip solder of desired thickness, rolling pass working modulus 20 ~ 40%; Bar-shaped alloy rolling is drawn into the filament solder of required diameter, drawing passes working modulus 15 ~ 35%;
5th step, to enter in 850 ~ 600 DEG C of vacuum resistance furnaces diffusion annealing 8 ~ 12 hours, can obtain satisfactory welding wire or weld tabs by the band shape of shaping or brazing wire.
In order to further reduce the fusing point of solder, improve the mobility of solder, reduce the volatilization of zinc in solder, need in copper-zinc solder to increase tin and silicon, then the first step can be replaced simultaneously:
The first step, prepares the alloy cylinder ingot that percentage by weight is zinc 35.5 ~ 39.94, copper 60 ~ 62, tin 0.05 ~ 2.0, silicon 0.01 ~ 0.5
First silicon, tin are become intermediate alloy A1 and A2 with copper weld pool respectively, in described intermediate alloy A1, the weight ratio of copper and silicon is 83:17; In described intermediate alloy A2, the weight ratio of copper and tin is 84.5:15.5;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy A1 and intermediate alloy A2, cover by complex salt after it fully fuses; Treat that it fully fuses, after molten metal temperature is down to 950 ~ 1050 DEG C, add metallic zinc; After abundant fusion, by static for molten metal 20 ~ 30 minutes, pour into the cylindrical shape ingot casting of external diameter 95mm, height 355mm, endoporus 30 ~ 60mm; Cylindrical shape ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use.
In order to reduce the fusing point of solder, improve the mobility of solder, when only increasing tin in copper-zinc solder, the first step can be replaced:
The first step, prepares the alloy cylinder that percentage by weight is zinc 36 ~ 39.95, copper 60 ~ 62, tin 0.05 ~ 2.0
First tin is become intermediate alloy with copper weld pool by ingot, and in described intermediate alloy, the weight ratio of copper and tin is 84.5:15.5;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy, cover by complex salt after it fully fuses; Treat that it fully fuses, after molten metal temperature is down to 950 ~ 1050 DEG C, add metallic zinc; After abundant fusion, by static for molten metal 20 ~ 30 minutes, pour into the cylindrical shape ingot casting of external diameter 95mm, height 355mm, endoporus 30 ~ 60mm; Cylindrical shape ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use.
In order to reduce the volatilization of zinc in solder, when only increasing silicon in copper-zinc solder, the first step can be replaced:
The first step, prepares the alloy circle that percentage by weight is zinc 37.5 ~ 39.99, copper 60 ~ 62, silicon 0.01 ~ 0.5
First silicon is become intermediate alloy with copper weld pool by cylinder ingot, and the weight ratio of described intermediate alloy copper and silicon is 83:17;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy, cover by complex salt after it fully fuses; Treat that it fully fuses, after molten metal temperature is down to 950 ~ 1050 DEG C, add metallic zinc; After abundant fusion, by static for molten metal 20 ~ 30 minutes, pour into the cylindrical shape ingot casting of external diameter 95mm, height 355mm, endoporus 30 ~ 60mm; Cylindrical shape ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use.
Described complex salt by dewatering borax and boric anhydride formulated according to the weight ratio of 7:3.
The invention has the advantages that simple operation, good stability and cost is lower.Solve the problem that existing high fragility copper-zinc solder is difficult to be processed into welding wire, weld tabs, copper-zinc solder can be processed into the welding wire of diameter≤2.5mm or the weld tabs of thickness≤0.3mm by the inventive method, meets the requirement of soldering production technology.
Accompanying drawing explanation
Fig. 1 is ormolu binary phase diagraml.
Fig. 2 is the micro-organization chart of the sheet of copper spelter solder that embodiment 1 obtains.
Detailed description of the invention
Preparation method of the present invention is described in detail by following examples.
embodiment 1: preparation GB solder HL102, Cu48Zn52
The first step, prepares the cylinder ingot that percentage by weight is Zn 38, Cu 62
Take 310 kilograms of cathode coppers, 198 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 30, the cylindrical shape ingot casting that 1050 ~ 1100 DEG C of cast obtain external diameter 95mm, diameter of bore 50mm, height 355mm; Ingot casting is carried out homogenizing annealing after 6 hours in 650 ~ 700 DEG C of chamber type electric resistance furnaces, and roughing becomes external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 60mm;
Second step, prepares the alloy cast ingot that percentage by weight is Cu 30, Zn 70
Take 110 kilograms of cathode coppers, 265 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 1050 ~ 1100 DEG C, and cast obtains diameter 65mm, the cylindrical ingot of high 375mm 30; Cylindrical ingot is entered 600 ~ 650 DEG C of annealing in resistance furnace and, after 5 hours, ingot casting is processed as diameter 60mm, the ingot casting of high 360mm;
3rd step, puts into the endoporus of cylinder ingot by ingot casting, axially add 120 ~ 150t pressure, and the swelling of ingot casting jumping-up forms composite ingot;
4th step, if need to prepare weld tabs, the chamber type electric resistance furnace preheating of composite ingot being put into 680 ~ 700 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder made-up belt that 55 mm are wide, 6mm is thick; After online annealing, strip brazing material is through repeatedly rolling---annealing, and (rolling pass working modulus 25% during more than tape thickness 3mm, between annealing temperature 680 ~ 700 DEG C to be prepared into 0.3 mm thickness band; Rolling pass working modulus 35% time between tape thickness 1 ~ 3mm, between annealing temperature 650 ~ 680 DEG C; Rolling pass working modulus 30% during tape thickness 0.5 ~ below 1mm, between annealing temperature 600 ~ 620 DEG C; Rolling pass working modulus 22% during below tape thickness 0.5mm, between annealing temperature 560 ~ 580 DEG C);
If need to prepare welding wire, the chamber type electric resistance furnace preheating of composite ingot being put into 680 ~ 700 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder rod base of diameter 16mm; After online annealing, bar-shaped solder is through repeatedly rolling---annealing---drawing---annealing, and (rolling pass working modulus 15% during more than diameter of rod 10mm, between annealing temperature 680 ~ 700 DEG C to be prepared into 2.5 mm filaments; Rolling pass reduction 20% time between diameter of rod 10 ~ 6.3mm, between annealing temperature 650 ~ 680 DEG C; Drawing passes working modulus 25% time between filament diameter 6.3 ~ 3mm, between annealing temperature 600 ~ 620 DEG C; During filament diameter 2.65mm, with the annealing temperature of 480 ~ 500 DEG C; Finally pull to 2.5mm).
5th step, the band shape shape the 4th step or brazing wire to enter in 750 DEG C of vacuum resistance furnaces diffusion annealing 10 hours, and vacuum 30pa, can obtain the finished product welding wire of diameter 2.5mm or the finished product weld tabs of thickness 0.3mm.Fig. 2 sees in the micro-organization chart of finished product weld tabs.
embodiment 2: preparation GB solder HL103, Cu54Zn46
The first step, prepares the cylinder ingot that percentage by weight is Zn 40, Cu 60
Take 310 kilograms of cathode coppers, 215 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 30, the cylindrical shape ingot casting that 1050 ~ 1100 DEG C of cast obtain external diameter 95mm, diameter of bore 30mm, height 355mm; Ingot casting is carried out homogenizing annealing after 6 hours in 650 ~ 700 DEG C of chamber type electric resistance furnaces, and roughing becomes external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40mm;
Second step, prepares the alloy cast ingot that percentage by weight is Cu 30, Zn 70
Take 110 kilograms of cathode coppers, 268 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 1050 ~ 1100 DEG C, and cast obtains diameter 45mm, the cylindrical ingot of high 375mm 30; Cylindrical ingot is entered 600 ~ 650 DEG C of annealing in resistance furnace and, after 5 hours, ingot casting is processed as diameter 40mm, the ingot casting of high 360mm;
3rd step, puts into the endoporus of cylinder ingot by ingot casting, axially add 120 ~ 150t pressure, and the swelling of ingot casting jumping-up forms composite ingot;
4th step, if need to prepare weld tabs, the chamber type electric resistance furnace preheating of composite ingot being put into 680 ~ 700 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder made-up belt that 35 mm are wide, 6mm is thick; After online annealing, strip brazing material is through repeatedly rolling---annealing, and (rolling pass working modulus 25% during more than tape thickness 3mm, between annealing temperature 680 ~ 700 DEG C to be prepared into 0.3 mm thickness band; Rolling pass working modulus 35% time between tape thickness 1 ~ 3mm, between annealing temperature 650 ~ 680 DEG C; Rolling pass working modulus 30% during tape thickness 0.5 ~ below 1mm, between annealing temperature 600 ~ 620 DEG C; Rolling pass working modulus 22% during below tape thickness 0.5mm, between annealing temperature 560 ~ 580 DEG C);
If need to prepare welding wire, the chamber type electric resistance furnace preheating of composite ingot being put into 680 ~ 700 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder rod base of diameter 16mm; After online annealing, bar-shaped solder is through repeatedly rolling---annealing---drawing---annealing, and (rolling pass working modulus 15% during more than diameter of rod 10mm, between annealing temperature 680 ~ 700 DEG C to be prepared into 2.0 mm filaments; Rolling pass reduction 20% time between diameter of rod 10 ~ 6.3mm, between annealing temperature 650 ~ 680 DEG C; Drawing passes working modulus 25% time between filament diameter 6.3 ~ 3mm, between annealing temperature 600 ~ 620 DEG C; During filament diameter 2.65mm, with the annealing temperature of 480 ~ 500 DEG C; Finally pull to 2.0mm).
5th step, the band shape shape the 4th step or brazing wire to enter in 750 DEG C of vacuum resistance furnaces diffusion annealing 8 hours, and vacuum 30pa, can obtain the finished product welding wire of diameter 2.0mm or the finished product weld tabs of thickness 0.3mm.
embodiment 3: prepare solder Cu51.5Zn46SnSi
The first step, preparing percentage by weight is zinc 38%, tin 2%, silicon 0.5%, and surplus is the alloy cylinder ingot of copper
Take 282 kilograms of cathode coppers, 187 kilograms of zinc,
10 kilogramstin,
2.5 kilogramsilicon, first becomes intermediate alloy A1 and A2 with copper weld pool respectively by tin lower to silicon higher for fusing point and fusing point, and wherein in intermediate alloy A1, the weight ratio of copper and silicon is 83:17; In intermediate alloy A2, the percentage by weight of copper and tin is 84.5:15.5;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy A1, cover by the complex salt of dewatering borax and boric anhydride preparation after it fully fuses, wherein the weight ratio of dewatering borax and boric anhydride is 7:3; Then add intermediate alloy A2, treat that it fully fuses, add metallic zinc after molten metal temperature is down to 950 ~ 1000 DEG C and fully fuse, melting later stage zincification adjustment copper zinc ratio; Be 1050 ~ 1100 DEG C by molten metal temperature stabilization, static 20 ~ 30 minutes, cast obtained 25, the cylindrical shape ingot casting of external diameter 95mm, height 355mm, diameter of bore 40mm; Cylindrical shape ingot casting to be entered in resistance furnace 650 ~ 700 DEG C and carry out homogenizing annealing 6 hours, roughing becomes external diameter 90mm, high 350mm, and the cylinder ingot of diameter of bore 50mm is for subsequent use;
Second step, prepares the alloy cast ingot that percentage by weight is Cu 36, Zn 64
Take 65 kilograms of cathode coppers, 116 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 1050 ~ 1100 DEG C, and cast obtains diameter 55mm, the cylindrical ingot of high 375mm 25; Cylindrical ingot is entered 650 ~ 700 DEG C of annealing in resistance furnace and, after 4 hours, ingot casting is processed as diameter 50mm, the ingot casting of high 360mm;
3rd step, puts into the endoporus of cylinder ingot by ingot casting, axially add 120 ~ 150t pressure, and the swelling of ingot casting jumping-up forms composite ingot;
4th step, if need to prepare weld tabs, the chamber type electric resistance furnace preheating of composite ingot being put into 780 ~ 800 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder made-up belt that 55 mm are wide, 6mm is thick; After online annealing, strip brazing material is through repeatedly rolling---annealing, and (rolling pass working modulus 28% during more than tape thickness 3mm, between annealing temperature 780 ~ 800 DEG C to be prepared into the thick strip of 0.3 mm; Rolling pass working modulus 35% time between tape thickness 1 ~ 3mm, between annealing temperature 750 ~ 780 DEG C; Rolling pass working modulus 30% during tape thickness 0.5 ~ below 1mm, between annealing temperature 700 ~ 730 DEG C; Rolling pass working modulus 22% during below tape thickness 0.5mm, between annealing temperature 660 ~ 690 DEG C);
If need to prepare welding wire, the chamber type electric resistance furnace preheating of composite ingot being put into 780 ~ 800 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder rod base of diameter 16mm; After online annealing, bar-shaped solder is through repeatedly rolling---annealing---drawing---annealing, and (rolling pass working modulus 15% during more than diameter of rod 10mm, between annealing temperature 780 ~ 800 DEG C to be prepared into 2.5 mm filaments; Rolling pass reduction 20% time between diameter of rod 10 ~ 6.3mm, between annealing temperature 750 ~ 780 DEG C; Drawing passes working modulus 25% time between filament diameter 6.3 ~ 3mm, between annealing temperature 700 ~ 730 DEG C; During filament diameter 2.65mm, with the annealing temperature of 660 ~ 690 DEG C; Finally pull to 2.5mm).
5th step, the band shape shape the 4th step or brazing wire to enter in 810 DEG C of vacuum resistance furnaces diffusion annealing 10 hours, and vacuum 30Pa, can obtain the finished product welding wire of diameter 2.5mm or the finished product weld tabs of thickness 0.3mm.
embodiment 4: preparation GB solder HL101, Cu36Zn64
The first step, prepares the cylinder ingot that percentage by weight is Zn 38, Cu 62
Take 300 kilograms of cathode coppers, 190 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 35, the cylindrical shape ingot casting that 1050 ~ 1100 DEG C of cast obtain external diameter 95mm, diameter of bore 60mm, height 355mm; Ingot casting is carried out homogenizing annealing after 6 hours in 650 ~ 700 DEG C of chamber type electric resistance furnaces, and roughing becomes external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 70mm;
Second step, prepares the alloy cast ingot that percentage by weight is Cu 20, Zn 80
Take 90 kilograms of cathode coppers, 360 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 1050 ~ 1100 DEG C, and cast obtains diameter 75mm, the cylindrical ingot of high 375mm 35; Cylindrical ingot is entered 450 ~ 500 DEG C of annealing in resistance furnace and, after 8 hours, ingot casting is processed as diameter 70mm, the ingot casting of high 360mm;
3rd step, puts into the endoporus of cylinder ingot by ingot casting, axially add 120 ~ 150t pressure, and the swelling of ingot casting jumping-up forms composite ingot;
4th step, if need to prepare weld tabs, the chamber type electric resistance furnace preheating of composite ingot being put into 550 ~ 580 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder made-up belt that 55 mm are wide, 6mm is thick; After online annealing, strip brazing material is through repeatedly rolling---annealing, and (rolling pass working modulus 25% during more than tape thickness 3mm, between annealing temperature 550 ~ 580 DEG C to be prepared into the thick strip of 0.3 mm; Rolling pass working modulus 35% time between tape thickness 1 ~ 3mm, between annealing temperature 520 ~ 560 DEG C; Rolling pass working modulus 30% during tape thickness 0.5 ~ below 1mm, between annealing temperature 470 ~ 510 DEG C; Rolling pass working modulus 22% during below tape thickness 0.5mm, between annealing temperature 430 ~ 470 DEG C);
If need to prepare welding wire, the chamber type electric resistance furnace preheating of composite ingot being put into 550 ~ 580 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder rod base of diameter 16mm; After online annealing, bar-shaped solder is through repeatedly rolling---annealing---drawing---annealing, and (rolling pass working modulus 15% during more than diameter of rod 10mm, between annealing temperature 550 ~ 580 DEG C to be prepared into 2.5 mm filaments; Rolling pass reduction 20% time between diameter of rod 10 ~ 6.3mm, between annealing temperature 520 ~ 560 DEG C; Drawing passes working modulus 25% time between filament diameter 6.3 ~ 3mm, between annealing temperature 470 ~ 510 DEG C; During filament diameter 2.65mm, with the annealing temperature of 430 ~ 470 DEG C; Finally pull to 2.5mm).
5th step, the band shape shape the 4th step or brazing wire to enter in 650 DEG C of vacuum resistance furnaces diffusion annealing 10 hours, and vacuum 20Pa, can obtain the finished product welding wire of diameter 2.5mm or the finished product weld tabs of thickness 0.3mm.
embodiment 5: prepare solder Cu54Zn45Sn
The first step, preparing percentage by weight is zinc 37%, tin 1%, and surplus is the alloy cylinder ingot of copper
Take 293 kilograms of cathode coppers, 182 kilograms of zinc,
5 kilogramstin, first becomes intermediate alloy A2 by tin lower for fusing point with copper weld pool, and in A2, the percentage by weight of copper and tin is 84.5:15.5;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy A2, treat that it fully fuses, add metallic zinc after molten metal temperature is down to 950 ~ 1000 DEG C and fully fuse, melting later stage zincification adjustment copper zinc ratio; Be 1050 ~ 1100 DEG C by molten metal temperature stabilization, static 20 ~ 30 minutes, cast obtained 24, the cylindrical shape ingot casting of external diameter 95mm, height 355mm, diameter of bore 33mm; Cylindrical shape ingot casting to be entered in resistance furnace 700 ~ 750 DEG C and carry out homogenizing annealing 6 hours, roughing becomes external diameter 90mm, high 350mm, and the cylinder ingot of diameter of bore 43mm is for subsequent use;
Second step, prepares the alloy cast ingot that percentage by weight is Cu 30, Zn 70
Take 105 kg cathode copper, 256 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 1050 ~ 1100 DEG C, and cast obtains diameter 48mm, the cylindrical ingot of high 375mm 24; Cylindrical ingot is entered 600 ~ 650 DEG C of annealing in resistance furnace and, after 5 hours, ingot casting is processed as diameter 43mm, the ingot casting of high 360mm;
3rd step, puts into the endoporus of cylinder ingot by ingot casting, axially add 120 ~ 150t pressure, and the swelling of ingot casting jumping-up forms composite ingot;
4th step, if need to prepare weld tabs, the chamber type electric resistance furnace preheating of composite ingot being put into 680 ~ 700 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder made-up belt that 35 mm are wide, 6mm is thick; After online annealing, strip brazing material is through repeatedly rolling---annealing, and (rolling pass working modulus 25% during more than tape thickness 3mm, between annealing temperature 680 ~ 700 DEG C to be prepared into 0.3 mm thickness band; Rolling pass working modulus 35% time between tape thickness 1 ~ 3mm, between annealing temperature 650 ~ 680 DEG C; Rolling pass working modulus 30% during tape thickness 0.5 ~ below 1mm, between annealing temperature 600 ~ 620 DEG C; Rolling pass working modulus 22% during below tape thickness 0.5mm, between annealing temperature 560 ~ 580 DEG C);
If need to prepare welding wire, the chamber type electric resistance furnace preheating of composite ingot being put into 680 ~ 700 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder rod base of diameter 16mm; After online annealing, bar-shaped solder is through repeatedly rolling---annealing---drawing---annealing, and (rolling pass working modulus 15% during more than diameter of rod 10mm, between annealing temperature 680 ~ 700 DEG C to be prepared into 2.0 mm filaments; Rolling pass reduction 20% time between diameter of rod 10 ~ 6.3mm, between annealing temperature 650 ~ 680 DEG C; Drawing passes working modulus 25% time between filament diameter 6.3 ~ 3mm, between annealing temperature 600 ~ 620 DEG C; During filament diameter 2.65mm, with the annealing temperature of 480 ~ 500 DEG C; Finally pull to 2.0mm).
5th step, the band shape shape the 4th step or brazing wire to enter in 750 DEG C of vacuum resistance furnaces diffusion annealing 8 hours, and vacuum 30pa, can obtain the finished product welding wire of diameter 2.0mm or the finished product weld tabs of thickness 0.3mm.
embodiment 6: prepare solder Cu53.8Zn46Si
The first step, preparing percentage by weight is zinc 37.8%, silicon 0.2%, and surplus is the alloy cylinder ingot of copper
Take 276.1 kilograms of cathode coppers, 173 kilograms of zinc, 0.9 kilogram of silicon, first silicon higher for fusing point is become intermediate alloy A1 with copper weld pool, wherein in intermediate alloy A1, the weight ratio of copper and silicon is 83:17;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy A1, cover by the complex salt of dewatering borax and boric anhydride preparation after it fully fuses, wherein the weight ratio of dewatering borax and boric anhydride is 7:3; Add metallic zinc after molten metal temperature is down to 950 ~ 1000 DEG C fully to fuse, melting later stage zincification adjustment copper zinc ratio; Be 1050 ~ 1100 DEG C by molten metal temperature stabilization, static 20 ~ 30 minutes, cast obtained 25, the cylindrical shape ingot casting of external diameter 95mm, height 355mm, diameter of bore 38mm; Cylindrical shape ingot casting to be entered in resistance furnace 650 ~ 700 DEG C and carry out homogenizing annealing 6 hours, roughing becomes external diameter 90mm, high 350mm, and the cylinder ingot of diameter of bore 48mm is for subsequent use;
Second step, prepares the alloy cast ingot that percentage by weight is Cu 36, Zn 64
Take 69 kilograms of cathode coppers, 126 kilograms of zinc, copper is melted in intermediate frequency furnace, temperature adds metallic zinc after reaching 1100 ~ 1200 DEG C, abundant fusion covers by the complex salt that dewatering borax and boric anhydride are prepared afterwards, wherein the weight ratio of dewatering borax and boric anhydride is 7:3, melting later stage zincification adjustment copper zinc ratio; Molten metal temperature is reduced to 1050 ~ 1100 DEG C, and cast obtains diameter 53mm, the cylindrical ingot of high 375mm 25; Cylindrical ingot is entered 650 ~ 700 DEG C of annealing in resistance furnace and, after 4 hours, ingot casting is processed as diameter 48mm, the ingot casting of high 360mm;
3rd step, puts into the endoporus of cylinder ingot by ingot casting, axially add 120 ~ 150t pressure, and the swelling of ingot casting jumping-up forms composite ingot;
4th step, if need to prepare weld tabs, the chamber type electric resistance furnace preheating of composite ingot being put into 780 ~ 800 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder made-up belt that 55 mm are wide, 6mm is thick; After online annealing, strip brazing material is through repeatedly rolling---annealing, and (rolling pass working modulus 28% during more than tape thickness 3mm, between annealing temperature 780 ~ 800 DEG C to be prepared into the thick strip of 0.3 mm; Rolling pass working modulus 35% time between tape thickness 1 ~ 3mm, between annealing temperature 750 ~ 780 DEG C; Rolling pass working modulus 30% during tape thickness 0.5 ~ below 1mm, between annealing temperature 700 ~ 730 DEG C; Rolling pass working modulus 22% during below tape thickness 0.5mm, between annealing temperature 660 ~ 690 DEG C);
If need to prepare welding wire, the chamber type electric resistance furnace preheating of composite ingot being put into 780 ~ 800 DEG C carried out Isothermal Extrusion after 4 hours, was squeezed into the solder rod base of diameter 16mm; After online annealing, bar-shaped solder is through repeatedly rolling---annealing---drawing---annealing, and (rolling pass working modulus 15% during more than diameter of rod 10mm, between annealing temperature 780 ~ 800 DEG C to be prepared into 2.5 mm filaments; Rolling pass reduction 20% time between diameter of rod 10 ~ 6.3mm, between annealing temperature 750 ~ 780 DEG C; Drawing passes working modulus 25% time between filament diameter 6.3 ~ 3mm, between annealing temperature 700 ~ 730 DEG C; During filament diameter 2.65mm, with the annealing temperature of 660 ~ 690 DEG C; Finally pull to 2.5mm).
5th step, the band shape shape the 4th step or brazing wire to enter in 810 DEG C of vacuum resistance furnaces diffusion annealing 10 hours, and vacuum 30Pa, can obtain the finished product welding wire of diameter 2.5mm or the finished product weld tabs of thickness 0.3mm.
Above embodiment is only the preferred embodiment for explaining the present invention, not does any pro forma restriction to the present invention, and all any modifications done under the invention or change all belong to the scope of protection of the invention.
Claims (5)
1. a preparation method for high fragility copper zinc welding rod/weld tabs, is characterized in that comprising the steps:
The first step, prepares the alloy cylinder ingot that percentage by weight is zinc 38 ~ 40, copper 60 ~ 62
Metallic copper is entered intermediate frequency furnace fusing, when temperature reaches 1100 ~ 1200 DEG C, add metallic zinc, fully cover by complex salt after fusion; The cylindrical shape ingot casting obtaining external diameter 95mm, height 355mm, endoporus 30 ~ 60mm is poured into a mould when molten metal temperature being reduced to 1050-1100 DEG C; Ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use;
Second step, prepares the alloy cast ingot that percentage by weight is zinc 64 ~ 80, copper 20 ~ 36
Metallic copper is entered intermediate frequency furnace fusing, when temperature reaches 1100 ~ 1200 DEG C, add metallic zinc, fully cover by complex salt after fusion; The cylindrical ingot obtaining external diameter 35 ~ 65mm, height 375mm is poured into a mould when molten metal temperature being reduced to 1050 ~ 1100 DEG C; Cylindrical ingot is entered 450 ~ 700 DEG C of annealing in resistance furnace and, after 3 ~ 8 hours, be processed into external diameter identical with cylinder ingot endoporus, the ingot casting of high 360mm;
3rd step, is axially pressed into ingot casting in the endoporus of cylinder ingot and forms composite ingot;
4th step, enters composite ingot in resistance furnace that 550 ~ 780 DEG C of preheatings are after 4 hours, and compound Isothermal Extrusion becomes bar-shaped or banded alloy; After online annealing, banded alloy rolling becomes the strip solder of desired thickness, rolling pass working modulus 20 ~ 40%; Bar-shaped alloy rolling is drawn into the filament solder of required diameter, drawing passes working modulus 15 ~ 35%;
5th step, to enter in 850 ~ 600 DEG C of vacuum resistance furnaces diffusion annealing 8 ~ 12 hours, can obtain satisfactory welding wire or weld tabs by the band shape of shaping or brazing wire.
2. the preparation method of high fragility copper zinc welding rod/weld tabs according to claim 1, is characterized in that: when increasing tin and silicon in copper-zinc solder, the first step replaces with:
The first step, prepares the alloy cylinder ingot that percentage by weight is zinc 35.5 ~ 39.94, copper 60 ~ 62, tin 0.05 ~ 2.0, silicon 0.01 ~ 0.5
First silicon, tin are become intermediate alloy A1 and A2 with copper weld pool respectively, in described intermediate alloy A1, the weight ratio of copper and silicon is 83:17; In described intermediate alloy A2, the weight ratio of copper and tin is 84.5:15.5;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy A1 and intermediate alloy A2, cover by complex salt after it fully fuses; Treat that it fully fuses, after molten metal temperature is down to 950 ~ 1050 DEG C, add metallic zinc; After abundant fusion, by static for molten metal 20 ~ 30 minutes, pour into the cylindrical shape ingot casting of external diameter 95mm, height 355mm, endoporus 30 ~ 60mm; Cylindrical shape ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use.
3. the preparation method of high fragility copper zinc welding rod/weld tabs according to claim 1, is characterized in that: when increasing tin in copper-zinc solder, the first step replaces with:
The first step, prepares the alloy cylinder ingot that percentage by weight is zinc 36 ~ 39.95, copper 60 ~ 62, tin 0.05 ~ 2.0
First tin is become intermediate alloy with copper weld pool, in described intermediate alloy, the weight ratio of copper and tin is 84.5:15.5;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy, cover by complex salt after it fully fuses; Treat that it fully fuses, after molten metal temperature is down to 950 ~ 1050 DEG C, add metallic zinc; After abundant fusion, by static for molten metal 20 ~ 30 minutes, pour into the cylindrical shape ingot casting of external diameter 95mm, height 355mm, endoporus 30 ~ 60mm; Cylindrical shape ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use.
4. the preparation method of high fragility copper zinc welding rod/weld tabs according to claim 1, is characterized in that: when increasing silicon in copper-zinc solder, the first step replaces with:
The first step, prepares the alloy cylinder ingot that percentage by weight is zinc 37.5 ~ 39.99, copper 60 ~ 62, silicon 0.01 ~ 0.5
First silicon is become intermediate alloy with copper weld pool, the weight ratio of described intermediate alloy copper and silicon is 83:17;
Remaining copper is entered intermediate frequency furnace fusing, when temperature reaches 1150 ~ 1300 DEG C, add intermediate alloy, cover by complex salt after it fully fuses; Treat that it fully fuses, after molten metal temperature is down to 950 ~ 1050 DEG C, add metallic zinc; After abundant fusion, by static for molten metal 20 ~ 30 minutes, pour into the cylindrical shape ingot casting of external diameter 95mm, height 355mm, endoporus 30 ~ 60mm; Cylindrical shape ingot casting to be entered in resistance furnace 450 ~ 750 DEG C of annealing 3 ~ 8 hours, be processed into external diameter 90mm, high 350mm, the cylinder ingot of diameter of bore 40 ~ 70mm is for subsequent use.
5. the preparation method of the high fragility copper zinc welding rod/weld tabs according to any one of claim 1,2,3 or 4, is characterized in that: described complex salt by dewatering borax and boric anhydride formulated according to the weight ratio of 7:3.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066999A (en) * | 1991-05-20 | 1992-12-16 | 江苏工学院 | Silver-free copper-based brazing filler metal |
| CN1408503A (en) * | 2001-09-21 | 2003-04-09 | 贝尔肯霍夫有限公司 | Welding electrode for spark cutting |
| CN1608790A (en) * | 2004-11-24 | 2005-04-27 | 哈尔滨工业大学 | High-plasticity Cu-P brazing filler alloy and its prepn |
| CN1652925A (en) * | 2002-04-18 | 2005-08-10 | 阿尔科公司 | Ultra-longlife, high formability brazing sheet |
| CN101913036A (en) * | 2010-09-08 | 2010-12-15 | 郑州机械研究所 | CuZnTi solder for soldering diamond tool |
| CN102862003A (en) * | 2012-10-08 | 2013-01-09 | 佛山市泓实机械制造有限公司 | Silver-free copper based solder and preparation method thereof |
| CN102896438A (en) * | 2012-10-22 | 2013-01-30 | 王志祥 | Copper-zinc solder and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6056775B2 (en) * | 1982-11-24 | 1985-12-11 | 日本鉱業株式会社 | Copper alloy for welded pipes |
| DE10308778B3 (en) * | 2003-02-28 | 2004-08-12 | Wieland-Werke Ag | Lead-free brass with superior notch impact resistance, used in widely ranging applications to replace conventional brasses, has specified composition |
| DE102004058318B4 (en) * | 2004-12-02 | 2006-09-28 | Diehl Metall Stiftung & Co.Kg | Use of a copper-zinc alloy |
-
2013
- 2013-09-26 CN CN201310443750.1A patent/CN103480987B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066999A (en) * | 1991-05-20 | 1992-12-16 | 江苏工学院 | Silver-free copper-based brazing filler metal |
| CN1408503A (en) * | 2001-09-21 | 2003-04-09 | 贝尔肯霍夫有限公司 | Welding electrode for spark cutting |
| CN1652925A (en) * | 2002-04-18 | 2005-08-10 | 阿尔科公司 | Ultra-longlife, high formability brazing sheet |
| CN1608790A (en) * | 2004-11-24 | 2005-04-27 | 哈尔滨工业大学 | High-plasticity Cu-P brazing filler alloy and its prepn |
| CN101913036A (en) * | 2010-09-08 | 2010-12-15 | 郑州机械研究所 | CuZnTi solder for soldering diamond tool |
| CN102862003A (en) * | 2012-10-08 | 2013-01-09 | 佛山市泓实机械制造有限公司 | Silver-free copper based solder and preparation method thereof |
| CN102896438A (en) * | 2012-10-22 | 2013-01-30 | 王志祥 | Copper-zinc solder and preparation method thereof |
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