CN101719527B - Production technique of copper strips for solar modules - Google Patents
Production technique of copper strips for solar modules Download PDFInfo
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- CN101719527B CN101719527B CN2009101547043A CN200910154704A CN101719527B CN 101719527 B CN101719527 B CN 101719527B CN 2009101547043 A CN2009101547043 A CN 2009101547043A CN 200910154704 A CN200910154704 A CN 200910154704A CN 101719527 B CN101719527 B CN 101719527B
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Abstract
The invention discloses a production technique of copper strips for solar modules, which belongs to the technical field of nonferrous metal processing and comprises the following steps: drawing-up of continuous-casting oxygen-free copper bar: using high-quality electrolytic copper as the raw material, melting at 1150+/-10 DEG C, keeping the temperature, covering the copper liquid surface with charcoal and graphite scales to ensure the vacuum state during melting, degassing on line, deoxidizing, stirring, and drawing up the copper bar with a tractor set in an on-off vacuum way; continuous extrusion of copper strip blanks: using oxygen-free copper rods as the raw material, producing copper strip blanks by using a continuous extruder set, cooling the extruded copper strip blanks through a vacuum oxidation-resisting pipe and a water tank, drying and coiling; and rough-rolling the copper strip blanks, medium-rolling, interstage annealing, finish rolling, degreasing, washing, annealing the finished product, washing, grinding the surface to passivate, and longitudinally cutting to obtain the finished product. The product of the invention has the advantages of high purity, low oxygen content and high electrical conductivity.
Description
Technical field
The invention belongs to technical field of nonferrous metal processing, relate in particular to a kind of production technology of copper strips for solar modules.
Background technology
Solar energy is the first-selected energy of human social as a kind of widely distributed, inexhaustible, nexhaustible green non-pollution clean energy resource; Solar cell is to utilize photoelectric effect with a kind of device of solar energy converting for electric energy.Copper strips is a base material of making the solar module tin-coated welding strip, and its performance requirement: conductance 〉=100%IACS, percentage elongation 〉=40%, tensile strength 240～260MPa, hardness HV≤50, oxygen content are less than 10ppm.Since its performance requirement height, oxygen content instability and processing difficulties, domestic demands import at present.
Summary of the invention
The invention provides a kind of production technology of copper strips for solar modules, for solving copper strips for solar modules performance requirement height, the difficult problem of oxygen content instability and processing difficulties, by strictness control oxygen content, optimize the copper strips for solar modules that the processing technology manufacturing substitutes import, constantly high-quality, the high performance demands of lifting are developed and are developed in order to adapt to the solar energy industry.
The technical scheme that the present invention takes is as follows, and a kind of production technology of copper strips for solar modules may further comprise the steps:
(1). the continuous up-casting oxygen-free copper bar: with the high-quality cathode copper is raw material, at 1150 ℃ ± 10 ℃ following melting and heat preservations, vacuum state when adopting charcoal and graphite scale covering copper liquid surface to guarantee fusing, and through online degasification, deoxidation, stirring, with drawing oxygen-free copper bar on the traction unit disengaging type vacuum;
(2). continuously extruded copper strips blank: with the oxygen-free copper bar is raw material, adopt continuously extruded unit production of copper made-up belt material, the continuous extruder rotating speed is 4～12r/min, cavity temperature 450-550 ℃, the made-up belt width can reach 320mm, copper strips blank extruded velocity: 5～15m/min, copper strips blank extrude after anti-oxidation pipe of vacuum and tank batch after cooling off, drying up;
(3). with above-mentioned continuously extruded copper strips blank, through roughing, in roll, intermediate annealing, finish rolling, cleaning by degreasing, finished products, the passivation of cleaning flour milling, slitting after cutting finished product.
Of the present invention further be provided with as follows:
Described online degasification, deoxidation, stirring, by online degasification deoxidation agitating device, in copper liquid, charge into 99.996% argon gas or nitrogen, by controlled rotation graphite shaft and rotor, the argon gas or the nitrogen of metering are pressed in the copper liquid and are dispersed as micro-bubble, it is dispersed in the copper liquid uniformly, source of the gas outlet pressure 0.5MPa, flow 1～1.25Nm
3/ n with drawing oxygen-free copper bar on the traction unit disengaging type vacuum, draws bar speed 500～1500mm/s then, and drawing shank diameter is Φ 20～Φ 30mm.
Described continuously extruded copper strips blank comprises the shape and size of appropriate design extended cavity, and pad is installed in the top of mould, and pad is a dumb-bell shape, increases spacer thickness, prolongs squeezing passage, guarantees the made-up belt quality.
Described roughing adopts the cold rolling unit of the reversible hydraulic AGC of four rollers that the copper strips blank is carried out roughing, and roughing processing passage is designed to: 16-9.5-6-4-2.8-2mm, and totally 5 passages, total working modulus is 70～90%.
Roll in described and adopt the cold rolling unit of the reversible hydraulic AGC of four rollers to roll during the copper strips blank is carried out, in roll the processing passage and be designed to: 2-1.5-1-0.8mm, totally 3 passages, total working modulus is 70～90%.
Described intermediate annealing adopts bright annealing equipment oxygen-free copper stripe to be carried out intermediate annealing, 250 ℃～400 ℃ of annealing temperatures, annealing time 2～6h.
Described finish rolling adopts the cold rolling unit of the reversible hydraulic AGC of six rollers that the copper strips blank is carried out finish rolling, the finish rolling Tension Control is at 5～15KN, finish rolling processing passage is designed to: 0.8-0.4-0.26-0.18-0.135-0.103mm, totally 5 passages, total working modulus is 25～80%, during finish rolling, adopt anti-oxidant special cooling-lubricant, prevent that copper strips is subjected to thermal oxidation.
Carry out cleaning by degreasing after the finish rolling, adopt the high-quality degreasing agent, its concentration 2～6%, and add 0.2～1% surfactant, temperature is controlled at 30 ℃～50 ℃, removes residual lubricating fluid and the various greasy dirt of copper strip surface, the control coiling tension guarantees annealing back copper strips quality.
Described finished products adopts the mode of bell-jar layering annealing, and the copper strips branch is placed on the heat-resistance stainless steel shelf, covers the bell-jar furnace shell, through the gaseous state sealing, takes out most air to 10 with vacuum pump
-3Pa charges into any one gas of the gaseous mixture of hydrogen, nitrogen or hydrogen and nitrogen, through three phases such as heat tracing cooling, 150 ℃～250 ℃ of annealing temperatures, annealing time 2～6h.
Clean the flour milling passivation behind the finished products, oxygen-free copper stripe after the annealing is entered cleaning flour milling passivation unit carry out surface treatment, utilize alkali lye that oxygen-free copper stripe is carried out degreasing, the degreasing liquid reserve tank adopts oily water separation technique, the sulfuric acid solution of employing 5%～10% carries out pickling to copper strips, employing is with the pin brush of 400～500 order abrasive materials, when scrubbing, the copper strips positive and negative is polished, polishing enters the hot water injection after extracting, then through 70 ℃～80 ℃, 0.2%～0.5% phenylpropyl alcohol triazole aqueous solution Passivation Treatment.
The present invention adopts such scheme to have following beneficial effect:
The purity height, oxygen content is low and conductance is high.Utilize copper liquid refining techniques, online degasification, deoxidation equipment and unique agitating device, guarantee blank purity height, oxygen content is low and conductance is high; The copper strips of the present invention's preparation: Cu+Ag 〉=99.98%, oxygen content are less than 8ppm, and conductance 〉=101%IACS reaches as high as 102%IACS.
2. adopt the design of unique mould and extended cavity, increase substantially the width and the quality of made-up belt.The present invention is by the shape and the thickness of appropriate design mould pad, improve the uniformity that flows, a big ratio and a big flakiness ratio expressing technique difficult problem have been solved, utilize 630 continuous extruders can produce the made-up belt of width at present for 320mm, made-up belt is soft attitude, can be directly rolling, can omit heating, mill operations such as face.
3. mechanical property and surface quality are superior.By road processing technology after the reasonable disposition, adopt roughing, in roll and small tension receiving coil finish rolling the uniformity and the stability of control tension force, the precision height of copper strips.Optimize annealing process simultaneously, guarantee the superior mechanical property of oxygen-free copper stripe, percentage elongation 〉=40%, tensile strength 240～260MPa, hardness HV≤50.
4, before finished products, carry out cleaning by degreasing, carry out PROCESS FOR TREATMENT such as degreasing, pickling, grinding and passivation behind the finished products, guarantee the no physics damage in its surface, its surface-brightening, do not have shake line, color and luster evenly, non-oxidation, no raffinate spot etc., and have cover waste water, a gas sampling system, a nonpollution environment.
Description of drawings:
Fig. 1 is the technological process of production figure of a kind of copper strips for solar modules of the present invention;
Fig. 2 is the structural representation of degasification deoxidation agitating device of the present invention;
Fig. 3 is cavity of the present invention and mould scheme of installation
Fig. 4 is the structural representation of mould of the present invention and pad.
Number in the figure: 1, smelting furnace; 2, holding furnace; 3, rotation graphite shaft and rotor; 40, cavity panel; 41, material blocking block, 42, extended cavity; 43, pad; 44, mould; 45, cover plate.
Embodiment:
As shown in Figure 1, adopting process scheme flow process of the present invention is as follows: the continuous up-casting oxygen-free copper bar---continuously extruded copper strips blank---roughing---in roll that------------finished products---cleans flour milling passivation---slitting is cut---packing warehouse-in to cleaning by degreasing in finish rolling in intermediate annealing
1. continuous up-casting oxygen-free copper bar
Selecting A level cathode copper for use is raw material, and after cathode copper preheating oven dry, 1150 ℃ ± 10 ℃ melt in smelting furnace, and crystallizer hydraulic pressure 2～4MPa, crystallizer leaving water temperature are controlled at 35 ℃～50 ℃, and holding furnace is incubated, 1150 ℃ ± 10 ℃ of copper liquid temperatures.Utilize online degasification deoxidation agitating device shown in Figure 2, charge into 99.996% argon gas or nitrogen in the copper liquid, by controlled rotation graphite shaft and rotor, the argon gas or the nitrogen of metering is pressed in the copper liquid and is dispersed as micro-bubble, it is dispersed in the copper liquid uniformly.Source of the gas outlet pressure 0.5MPa, flow 1～1.25Nm
3/ n.Copper liquid surface coverage is through the charcoal and the graphite scale of oven dry.With drawing oxygen-free copper bar on the traction unit disengaging type vacuum, oxygen-free copper bar enters take-up then.Draw bar speed 500～1500mm/s, drawing shank diameter is Φ 20～Φ 30mm, and the present invention adopts copper liquid refining techniques, online degasification, deoxidation equipment and unique agitating device, the oxygen-free copper bar of preparation: Cu+Ag 〉=99.98%, oxygen content is less than 8ppm, conductance 〉=101%IACS.
2. continuously extruded copper strips blank
With Φ 20～Φ 30mm oxygen-free copper bar is raw material, adopts the continuously extruded unit production of copper of TJL630 made-up belt material, production of copper made-up belt gauge lattice 320 * 15mm.
Oxygen-free copper bar is through after aligning, send between compact wheel and the squeegee roller, copper bar in the extruding race is sent into extrusion chamber continuously under the effect of frictional force, blank in cavity material blocking block front along circular motion, through zones such as fricting shearing deformed area, jumping-up deformed area, adhesioin zone, right-angle bending crush zones, enter cavity at last and extrude the copper strips blank by mould, in extrusion process, the continuous extruder rotating speed is 4～12r/min, cavity temperature 450-550 ℃, copper strips blank extruded velocity: 5～15m/min.Cool off, dry up through anti-oxidation pipe of vacuum and tank behind the copper strips blank extrusion die, batch to 20 ℃～30 ℃.
The present invention is in order to improve the mobile uniformity and the useful life of mould, reduce defectives such as " filling out discontented " and dimensional discrepancy are big, improved the structure of extended cavity 42 and pad 43, as shown in Figure 3, Figure 4, the design of the mould of uniqueness of the present invention and extended cavity comprises that cavity is made up of cavity panel 40, extended cavity 42, pad 43, mould 44 and cover plate 45; Pad 43 is installed in the top of mould 44, and pad 43 is a dumb-bell shape.The present invention is installed in pad 43 on the top of mould 44, increased squeezing passage, the shape of appropriate design pad 43, dumb-bell shape as shown in Figure 4 increases the limit portion size of pad 43 effectively, thereby reduce the difference of flowing velocity, by above-mentioned improvement, the width that the present invention produces made-up belt can reach 320mm, and made-up belt is soft attitude, can be directly rolling, thus heating omitted, mill operations such as face.Simultaneously, adopt the vacuum water device for cooling, make blank after high temperature is extruded, enter the vacuum tube cooling, in whole deformation process, cut off and the contacting of oxygen, avoid oxygen uptake, guarantee the copper strips low oxygen content.
3. roughing
Adopt the cold rolling unit of the reversible hydraulic AGC of four rollers that the copper strips blank is carried out roughing, be furnished with simultaneously that hydraulic pressure is depressed, hydraulic bending roll, segmentation cooling and device for automatically control thickness and plate shape automatic control equipment.The roughing pass reduction is controlled at 25%～50%, and present embodiment roughing processing passage is designed to: 16-9.5-6-4-2.8-2mm, and totally 5 passages, total working modulus is 70～90%.
4. roll in
Adopt the cold rolling unit of the reversible hydraulic AGC of four rollers to roll during the copper strips blank is carried out, be furnished with simultaneously that hydraulic pressure is depressed, hydraulic bending roll, segmentation cooling and device for automatically control thickness and plate shape automatic control equipment.Rolling the processing passage in the present embodiment is designed to: 2-1.5-1-0.8mm, and totally 3 passages, total working modulus is 70～90%.
5. intermediate annealing
With bright annealing equipment oxygen-free copper stripe is carried out intermediate annealing, 250 ℃～400 ℃ of annealing temperatures, annealing time 2～6h.
6. finish rolling
Adopt the cold rolling unit of the reversible hydraulic AGC of six rollers that the copper strips blank is carried out finish rolling, the finish rolling Tension Control is at 5～15KN, is furnished with simultaneously that hydraulic pressure is depressed, hydraulic bending roll, segmentation cooling and device for automatically control thickness and plate shape automatic control equipment.The anti-oxidant special cooling-lubricant of preferred employing prevents that copper strips is subjected to thermal oxidation.Present embodiment finish rolling processing passage is designed to: 0.8-0.4-0.26-0.18-0.135-0.103mm, and totally 5 passages, total working modulus is 25～80%.
7. cleaning by degreasing
Adopt the high-quality degreasing agent, its concentration 2～6%, and add 0.2～1% surfactant, and temperature is controlled at 30 ℃～50 ℃, removes residual lubricating fluid and the various greasy dirt of copper strip surface, and the control coiling tension guarantees annealing back copper strips quality.
8. finished products
Adopt the mode of bell-jar layering annealing, the copper strips branch is placed on the heat-resistance stainless steel shelf, cover the bell-jar furnace shell,, take out most air to 10 with vacuum pump through the gaseous state sealing
-3Pa charges into any one gas of the gaseous mixture of hydrogen, nitrogen or hydrogen and nitrogen, through three phases such as heat tracing coolings.150 ℃～250 ℃ of annealing temperatures, annealing time 2～6h.
9. clean the flour milling passivation
Oxygen-free copper stripe after the annealing is entered cleaning flour milling passivation unit carry out surface treatment.Utilize alkali lye that oxygen-free copper stripe is carried out ungrease treatment, the degreasing liquid reserve tank adopts oily water separation technique, can realize that waste oil reclaims, and guarantees degreasing effect.The sulfuric acid solution of employing 5%～10% carries out pickling to copper strips, adopts the pin brush with 400～500 order abrasive materials, when scrubbing, the copper strips positive and negative is polished, and makes its surface light more.Polishing enters the hot water injection after extracting, then through 70 ℃～80 ℃, 0.2%～0.5% phenylpropyl alcohol triazole aqueous solution Passivation Treatment.Machine row speed 10～100m/min, the steady state speed precision: ± 0.2%, uncoiling tension 0.34～5.04KN, coiling tension 0.51～7.56KN.Copper strips turriform degree after batching≤± 1mm, the fault amount≤± 0.5mm.
10. slitting is cut
To cut by slitter through the oxygen-free copper stripe of annealing in process, and adopt long distance, the separating and cutting process of cutting into slices more, and optimize drawing tension and distance, cutting width is 30～300mm.
11. packing warehouse-in
By national standard and customer requirements, product is carried out the detection of measuring mechanical property, electric performance test, dimensional tolerance, surface quality.Detect qualified back packing warehouse-in.
Claims (9)
1. the production technology of a copper strips for solar modules may further comprise the steps:
(1), the continuous up-casting oxygen-free copper bar: with the cathode copper is raw material, at 1150 ℃ ± 10 ℃ following melting and heat preservations, vacuum state when adopting charcoal and graphite scale covering copper liquid surface to guarantee fusing, and through online degasification, deoxidation, stir, described online degasification, deoxidation, stir, by online degasification deoxidation agitating device, in copper liquid, charge into 99.996% argon gas or nitrogen, by controlled rotation graphite shaft and rotor, be pressed into argon gas or nitrogen in the copper liquid and be dispersed as micro-bubble, it is dispersed in the copper liquid uniformly, source of the gas outlet pressure 0.5MPa, flow 1～1.25Nm
3/ h with drawing oxygen-free copper bar on the traction unit disengaging type vacuum, draws bar speed 500～1500mm/s then, and drawing shank diameter is Φ 20～Φ 30mm;
(2), continuously extruded copper strips blank: with the oxygen-free copper bar is raw material, adopt continuously extruded unit production of copper made-up belt material, the continuous extruder rotating speed is 4～12r/min, cavity temperature 450-550 ℃, the made-up belt width reaches 320mm, copper strips blank extruded velocity: 5～15m/min, copper strips blank extrude after anti-oxidation pipe of vacuum and tank batch after cooling off, drying up;
(3), with above-mentioned continuously extruded copper strips blank, through roughing, in roll, intermediate annealing, finish rolling, cleaning by degreasing, finished products, the passivation of cleaning flour milling, slitting after cutting finished product.
2. the production technology of a kind of copper strips for solar modules according to claim 1 is characterized in that: described continuously extruded copper strips blank, the shape and size of design extended cavity, pad is installed in the top of mould, pad is a dumb-bell shape, increases spacer thickness, prolongs squeezing passage.
3. the production technology of a kind of copper strips for solar modules according to claim 1, it is characterized in that: described roughing adopts the cold rolling unit of the reversible hydraulic AGC of four rollers that the copper strips blank is carried out roughing, roughing processing passage is designed to: 16-9.5-6-4-2.8-2mm, totally 5 passages, total working modulus is 70～90%.
4. the production technology of a kind of copper strips for solar modules according to claim 1, it is characterized in that: roll in described and adopt the cold rolling unit of the reversible hydraulic AGC of four rollers to roll during the copper strips blank is carried out, in roll processing passage be designed to: 2-1.5-1-0.8mm, totally 3 passages, total working modulus is 70～90%.
5. the production technology of a kind of copper strips for solar modules according to claim 1 is characterized in that: described intermediate annealing adopts bright annealing equipment oxygen-free copper stripe to be carried out intermediate annealing, 250 ℃～400 ℃ of annealing temperatures, annealing time 2～6h.
6. the production technology of a kind of copper strips for solar modules according to claim 1, it is characterized in that: described finish rolling adopts the cold rolling unit of the reversible hydraulic AGC of six rollers that the copper strips blank is carried out finish rolling, the finish rolling Tension Control is at 5～15KN, finish rolling processing passage is designed to: 0.8-0.4-0.26-0.18-0.135-0.103mm, totally 5 passages, total working modulus is 25～80%, during finish rolling, adopt anti-oxidant cooling-lubricant, prevent that copper strips is subjected to thermal oxidation.
7. the production technology of a kind of copper strips for solar modules according to claim 6, it is characterized in that: carry out cleaning by degreasing after the finish rolling, adopt degreasing agent, its concentration 2～6%, and add 0.2～1% surfactant, temperature is controlled at 30 ℃～50 ℃, removes residual lubricating fluid and the various greasy dirt of copper strip surface, the control coiling tension.
8. the production technology of a kind of copper strips for solar modules according to claim 1, it is characterized in that: described finished products adopts the mode of bell-jar layering annealing, the copper strips branch is placed on the heat-resistance stainless steel shelf, cover the bell-jar furnace shell, through the gaseous state sealing, take out most air to 10 with vacuum pump
-3Pa charges into any one gas of the gaseous mixture of hydrogen, nitrogen or hydrogen and nitrogen, through three phases such as heat tracing cooling, 150 ℃～250 ℃ of annealing temperatures, annealing time 2～6h.
9. the production technology of a kind of copper strips for solar modules according to claim 8, it is characterized in that: clean the flour milling passivation behind the finished products, oxygen-free copper stripe after the annealing is entered cleaning flour milling passivation unit carry out surface treatment, utilize alkali lye that oxygen-free copper stripe is carried out ungrease treatment, the degreasing liquid reserve tank adopts oily water separation technique, the sulfuric acid solution of employing 5%～10% carries out pickling to copper strips, employing is with the pin brush of 400～500 order abrasive materials, when scrubbing, the copper strips positive and negative is polished, after extracting, polishing enters the hot water injection, then through 70 ℃～80 ℃, 0.2%～0.5% phenylpropyl alcohol triazole aqueous solution Passivation Treatment, oven dry is batched.
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| CN1103612A (en) * | 1993-12-11 | 1995-06-14 | 山东烟台铜材厂 | Drawing-continuous casting-stretch process for producing oxygen-free copper pipe |
| CN1731534A (en) * | 2005-06-27 | 2006-02-08 | 江阴市电工合金有限公司 | Oxygen-free copper generatrix and its preparing method |
| CN101134276A (en) * | 2007-09-29 | 2008-03-05 | 绍兴市力博电缆有限公司 | Production technology of big-length oxygen-free copper stripe |
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