CN101519760A - Production method of 3003-brand cathode aluminum foil - Google Patents
Production method of 3003-brand cathode aluminum foil Download PDFInfo
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Abstract
The invention relates to a production method of 3003-brand cathode aluminum foil, which includes the following steps: a. raw materials are refined and rolled into a blank with the thickness of 6.5 mm to 8.5 mm; b. the blank obtained in step a is rolled into the blank with the thickness of 3.5 mm to 4.3 mm in a cooling mode to be uniformly annealed; c. the uniformly-annealed blank is rolled into the blank with the thickness of 0.3 mm to 0.5 mm in a cooling mode to be recrystallized and annealed; and d. the recrystallized-and-annealed blank is rolled into the 3003-brand cathode aluminum foil with the required thickness. The method of the invention enables the cost to be lower and the product quality to be better, the specific capacitance of the product is increased to be higher than 530 microfarads /cm<2>, and the highest specific capacitance can be 560 microfarads /cm<2>. The invention greatly improves the product competitive strength, reduces the disparity with abroad products, and makes a contribution for the trade progress.
Description
Technical field
The invention belongs to aluminum alloy materials and make the field, be specifically related to a kind of manufacture method of 3003 brand cathode aluminum foils.
Background technology
Along with the fast development of electronic technology, the packing density of complete electronic set and integrated degree are increasing, and electrolytic condenser just develops towards small volume, large vol, low cost, low impedance at high frequency direction as discrete component key, can not be integrated.Aluminum electrolytic capacitor with its excellent property, cheap, be easy to processing, advantage such as easy to use, be widely used.Because 3003 aluminum alloy materials have machining property well, etch resistant properties, heat dispersion, anti-electromagnetic interference performance, density is little and characteristics such as good mechanical performance, obtained the approval in market as the cathode aluminum foil of aluminium electrolutic capacitor, in the Cathode Foil of the various trades mark of aluminium alloy, its application percentage accounts for the domestic market more than 70%.
At present China's electrolytic condenser still lags behind international top-brand with the quality of cathode aluminum foil, is in particular in roughness and homogeneity, oxide thickness and homogeneity, surface microstructure and homogeneity, than aspects such as electric capacity are low.3003 of domestic production is that the alloy cathode aluminium foil has only 520 μ F/cm than electric capacity
2And unstable, and reached 600 μ F/cm abroad
2More than.Therefore, the ratio electric capacity that improves homemade cathode aluminum foil just seems very important.
Capacitance equation:
Wherein
C---electrical capacity (F); S---electrode area (m
2); D---dielectric thickness (m); ε
r---relative permittivity (relative permittivity of alumite is 7～8); ε
0---the specific inductivity of medium under vacuum state.
According to formula (1) as can be known, at the area S that increases cathode aluminum foil or when reducing dielectric layer thickness d, can obtain higher electrical capacity.Though can increase electrical capacity yet increase area simply, also increased the volume of electrical condenser simultaneously, therefore do not meet the requirement of electric equipment products miniaturization development.And, can go out a large amount of tunnels and Kong Keng in the cathode aluminum foil surface corrosion by corrosion technology, can under the prerequisite that does not increase even reduce cathode aluminum foil weight, greatly increase its surface-area, thereby increase electrical capacity.
The grain size of 3003 brand cathode aluminum foils has a significant impact corrosion, 3003 line aluminium alloys contain the Mn element, the degree of super saturation of casting plate solute element in sosoloid improves greatly, this is that alloy has the very strong cold energy power of crossing again, when cooling off fast, the concentration distribution of Mn is inhomogeneous, produces very big grain segregation, causes recrystal grain to be grown up seriously.Big crystal grain causes layering in process of rolling aluminum foil, the layering of aluminium foil can make cathode aluminum foil cause gradation etching again, and the result of gradation etching makes the material attenuate easily, and specific volume is reduced, and therefore requires 3003 brand cathode aluminum foil uniform crystal particles tiny.
At present also having some defectives, existing method in the production of cathode aluminum foil is directly to carry out recrystallization annealing after the casting, but the crystal grain of annealing back product is thick, causes gradation etching easily, causes specific volume to reduce, and directly influences the quality of product.And existing method need be cast into the electrolytic aluminum liquation aluminium ingot and carry out casting again after the remelting again, and technology is loaded down with trivial details, and has caused the waste of resource, and the production cost height does not meet the strategy of sustainable development.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of 3003 brand cathode aluminum foils, the ratio electric capacity of the cathode aluminum foil of being produced is improved, and cost decreases.
For achieving the above object, the present invention by the following technical solutions: a kind of manufacture method of 3003 brand cathode aluminum foils may further comprise the steps: a, raw material obtain the blank that thickness is 6.5～8.5mm after refining, casting; B, the blank that step a is obtained carry out homogenizing annealing after being cold-rolled to 3.5～4.3mm thickness, and the homogenizing annealing temperature is 450～480 ℃, and annealing time is 24～27 hours; C, the blank behind the homogenizing annealing is cold-rolled to 0.3～0.5mm thickness, carries out recrystallization annealing then, the temperature of recrystallization annealing is 275～330 ℃, and annealing time is 13～18 hours; D, the blank after the recrystallization annealing is rolled to 3003 brand cathode aluminum foil desired thicknesses gets final product.
Described step a is raw materials used to be the electrolytic aluminum liquation, the method for casting after the refining of employing electrolytic aluminum liquation.
The concrete steps of described step a are: the electrolytic aluminum liquation is delivered to smelting furnace, add the aluminium ingot that accounts for electrolytic aluminum liquation gross weight 20～40%, the control melt temperature is 750～780 ℃, and the mass percent of adjusting each elemental composition in the melt is: Si:0.1～0.15%, Fe:0.45～0.5%, Cu:0.1～0.15%, Mn:1.1～1.2%, Ti:0.02～0.04%, surplus are Al; Adopt pure nitrogen gas or pure argon to spray the refining agent refining in melt, stir, refining time is 8～10 minutes, leaves standstill then 15～25 minutes, removes the scum silica frost on aluminium liquid surface, pours into and leaves standstill in the stove, and it is 750～760 ℃ that the interior temperature of stove is left standstill in control; The aluminium liquid that leaves standstill in the stove is sent in the chute, and reverse adding aluminium titanium boron wire carries out grain refining, with pure nitrogen gas or pure argon aluminium liquid is carried out degassing processing then in degasification tank, adopts floamed ceramics filtrating piece that aluminium liquid is carried out filtration, purification after the degasification and handles; Aluminium liquid after the purification send the casting and rolling machine casting, and casting goes out the blank that thickness is 6.5～8.5mm.
The add-on of described aluminium titanium boron wire adds 2～3 ‰ of preceding aluminium liquid weight for it.
The rotating speed of graphite rotator is 120～180r/min in the described degasification tank.
Described refining agent is injection refining agent SY-PJ1, and add-on is for adjusting 0.1～0.4% of melt weight after the elemental composition.
The present invention has increased the process of homogenizing annealing, uneven eutectic structure in the ingot casting is distributed in matrix be tending towards even, the super saturated solid solution element is separated out from sosoloid, make crystal grain tiny evenly, to eliminate casting stress, improve ingot casting plasticity, reduce resistance to deformation, improve the tissue and the performance of converted products; Temperature when making recrystallization annealing simultaneously reduces greatly, has reduced energy consumption, has saved resource; The suitable temperature of control prevents that the too high appearance of temperature from influencing the burning and the superheating phenomenon of quality product when homogenizing annealing and recrystallization annealing; The present invention is the mode of the direct casting production of electrolytic aluminum liquation preferably, but because hydrogen content and dregginess are higher in the electrolytic aluminum liquation, need to take effective slagging-off, degasification measure in the casting production process, can adopt the mode that feeds nitrogen or argon gas degasification, slagging-off to the electrolytic aluminum liquation, nitrogen or argon gas form the bubble of a large amount of disperses in molten aluminium, bubble fully contacts with molten aluminium in floating-upward process, and gas in the aluminium liquid and inclusion are taken to aluminium liquid surface, reaches the purpose of degasification, slagging-off; Control graphite rotator rotating speed be because rotating speed when too low number of bubbles few, be unfavorable for degasification, cause the hydrogen richness height, the wearing and tearing of accelerating rotor caused secondary pollution to aluminium liquid when rotating speed was too fast, and rotating speed can cause too soon that molten aluminium splashes in the degasification tank, causes oxidative slagging; Adopt the direct casting production of electrolytic aluminum liquation to compare traditional casting and roll process and further shortened the flow process of producing again, saved the process of ingot casting and remelting, reduced energy consumption, also reduced facility investment, because the electrolytic aluminum liquation has higher temperature, also reduced the energy consumption of aluminium liquid insulation, compare traditional casting and roll process and reduced cost, also meet Sustainable development, made contribution for alleviating the exhausted day by day present situation of resource; Method of the present invention makes cost lower, and quality product is more excellent, and the ratio electric capacity of product is brought up to 530 μ F/cm
2More than, height can arrive 560 μ F/cm
2, improved competitiveness of product greatly, dwindled the gap with external product, also made contribution for the progress of industry.
Embodiment
Embodiment 1: 3003 brand cathode aluminum foils with 0.041mm thickness are example:
A, the electrolytic aluminum liquation is delivered to smelting furnace, add the aluminium ingot that accounts for electrolytic aluminum liquation gross weight 20%, the control melt temperature is 750 ℃, and the mass percent of adjusting each elemental composition in the melt is: Si:0.1%, Fe:0.5%, Cu:0.1%, Mn:1.1%, Ti:0.02%, surplus are Al; Adopt pure nitrogen gas in melt, to spray injection refining agent SY-PJ1 refining, the SY-PJ1 add-on is for adjusting 0.1% of melt weight after the elemental composition, stir, refining time is 8 minutes, left standstill then 15 minutes, remove the scum silica frost on aluminium liquid surface, pour into and leave standstill in the stove, it is 750 ℃ that the interior temperature of stove is left standstill in control; The aluminium liquid that leaves standstill in the stove is sent in the chute, reverse adding aluminium titanium boron wire carries out grain refining, the add-on of aluminium titanium boron wire adds 2 ‰ of preceding aluminium liquid weight for it, in degasification tank, aluminium liquid is carried out degassing processing then with pure nitrogen gas, the rotating speed of graphite rotator is 120r/min in the degasification tank, adopts floamed ceramics filtrating piece that aluminium liquid is carried out filtration, purification after the degasification and handles; Aluminium liquid after the purification send the casting and rolling machine casting, and casting goes out the blank that thickness is 6.5mm;
B, carry out homogenizing annealing after cast-rolling stock is cold-rolled to 3.5mm thickness, 450 ℃ of homogenizing annealing temperature, annealing time is 24h;
C, the blank behind the high temperature annealing is cold-rolled to 0.3mm through multi-pass, carries out recrystallization annealing then, the recrystallization annealing temperature is 275 ℃, and annealing time is 13h, and grain-size is 190 μ m;
D, the blank after the recrystallization annealing is rolled to the thickness of 0.041mm, cuts packing then, obtaining final thickness is the cathode aluminum foil product of 0.041mm.
Embodiment 2: 3003 brand cathode aluminum foils with 0.041mm thickness are example:
A, the electrolytic aluminum liquation is delivered to smelting furnace, add the aluminium ingot that accounts for electrolytic aluminum liquation gross weight 40%, the control melt temperature is 780 ℃, and the mass percent of adjusting each elemental composition in the melt is: Si:0.12%, Fe:0.48%, Cu:0.12%, Mn:1.15%, Ti:0.03%, surplus are Al; Adopt pure argon in melt, to spray injection refining agent SY-PJ1 refining, the SY-PJ1 add-on is for adjusting 0.4% of melt weight after the elemental composition, stir, refining time is 10 minutes, left standstill then 25 minutes, remove the scum silica frost on aluminium liquid surface, pour into and leave standstill in the stove, it is 760 ℃ that the interior temperature of stove is left standstill in control; The aluminium liquid that leaves standstill in the stove is sent in the chute, reverse adding aluminium titanium boron wire carries out grain refining, the add-on of aluminium titanium boron wire adds 3 ‰ of preceding aluminium liquid weight for it, in degasification tank, aluminium liquid is carried out degassing processing then with pure argon, the rotating speed of graphite rotator is 180r/min in the degasification tank, adopts floamed ceramics filtrating piece that aluminium liquid is carried out filtration, purification after the degasification and handles; Aluminium liquid after the purification send the casting and rolling machine casting, and casting goes out the blank that thickness is 8.5mm;
B, carry out homogenizing annealing after cast-rolling stock is cold-rolled to 4.3mm thickness, 480 ℃ of homogenizing annealing temperature, annealing time is 27h;
C, the blank behind the high temperature annealing is cold-rolled to 0.5mm through multi-pass, carries out recrystallization annealing then, the recrystallization annealing temperature is 330 ℃, and annealing time is 18h, and grain-size is 200 μ m;
D, the blank after the recrystallization annealing is rolled to the thickness of 0.041mm, cuts packing then, obtaining final thickness is the cathode aluminum foil product of 0.041mm.
Embodiment 3: 3003 brand cathode aluminum foils with 0.041mm thickness are example:
A, the electrolytic aluminum liquation is delivered to smelting furnace, add the aluminium ingot that accounts for electrolytic aluminum liquation gross weight 30%, the control melt temperature is 770 ℃, and the mass percent of adjusting each elemental composition in the melt is: Si:0.15%, Fe:0.45%, Cu:0.15%, Mn:1.2%, Ti:0.04%, surplus are Al; Adopt pure nitrogen gas in melt, to spray injection refining agent SY-PJ1 refining, the SY-PJ1 add-on is for adjusting 0.3% of melt weight after the elemental composition, stir, refining time is 9 minutes, left standstill then 20 minutes, remove the scum silica frost on aluminium liquid surface, pour into and leave standstill in the stove, it is 755 ℃ that the interior temperature of stove is left standstill in control; The aluminium liquid that leaves standstill in the stove is sent in the chute, reverse adding aluminium titanium boron wire carries out grain refining, the add-on of aluminium titanium boron wire adds 2.5 ‰ of preceding aluminium liquid weight for it, in degasification tank, aluminium liquid is carried out degassing processing then with pure nitrogen gas, the rotating speed of graphite rotator is 150r/min in the degasification tank, adopts floamed ceramics filtrating piece that aluminium liquid is carried out filtration, purification after the degasification and handles; Aluminium liquid after the purification send the casting and rolling machine casting, and casting goes out the blank that thickness is 7.5mm;
B, carry out homogenizing annealing after cast-rolling stock is cold-rolled to 3.9mm thickness, 470 ℃ of homogenizing annealing temperature, annealing time is 26h;
C, the blank behind the high temperature annealing is cold-rolled to 0.4mm through multi-pass, carries out recrystallization annealing then, the recrystallization annealing temperature is 300 ℃, and annealing time is 16h, and grain-size is 180 μ m;
D, the blank after the recrystallization annealing is rolled to the thickness of 0.041mm, cuts packing then, obtaining final thickness is the cathode aluminum foil product of 0.041mm.
The performance of embodiment 1 to embodiment 3 products obtained therefrom and the comparative data such as the following table 1 of prior art products performance:
Table 1
| Product | Tensile strength (MPa) | Unit elongation (%) | Than electric capacity (μ F/cm 2) |
| Embodiment 1 cathode aluminum foil product | 256 | 4.5 | 540 |
| Embodiment 2 cathode aluminum foil products | 248 | 4 | 530 |
| Embodiment 3 cathode aluminum foil products | 260 | 5 | 560 |
| 3003 brand cathode aluminum foils of domestic prior art 0.041mm thickness | 250 | 4 | 520 |
Find out obviously that by the data in the last table 1 the ratio electric capacity of the cathode aluminum foil that each embodiment of the present invention is prepared is all at 530 μ F/cm
2More than, Gao Keda 560 μ F/cm
2, the ratio electric capacity of the cathode aluminum foil of producing than domestic prior art is greatly improved, though also have gap with external product, has been a much progress of domestic industry.
The domestic prior art products that is compared does not have the process of homogenizing annealing in the preparation, directly carries out recrystallization annealing, and raw material adopts the method for aluminium ingot casting after remelting, melting.
Tensile strength and unit elongation use GB/T228-2002 " metallic substance tensile tests at room method " to measure.
Aluminium foil carries out chemical corrosion (corrosive water solution contains 25～50 gram HCL/ liters) by working condition, measures specific capacitance on CQ-A type large value capacitor bridge test instrument.
Claims (6)
1, a kind of manufacture method of 3003 brand cathode aluminum foils is characterized in that may further comprise the steps: a, raw material obtain the blank that thickness is 6.5～8.5mm after refining, casting; B, the blank that step a is obtained carry out homogenizing annealing after being cold-rolled to 3.5～4.3mm thickness, and the homogenizing annealing temperature is 450～480 ℃, and annealing time is 24～27 hours; C, the blank behind the homogenizing annealing is cold-rolled to 0.3～0.5mm thickness, carries out recrystallization annealing then, the temperature of recrystallization annealing is 275～330 ℃, and annealing time is 13～18 hours; D, the blank after the recrystallization annealing is rolled to 3003 brand cathode aluminum foil desired thicknesses gets final product.
2, the manufacture method of 3003 brand cathode aluminum foils as claimed in claim 1 is characterized in that: described step a is raw materials used to be the electrolytic aluminum liquation, the method for casting after the refining of employing electrolytic aluminum liquation.
3, the manufacture method of 3003 brand cathode aluminum foils as claimed in claim 2, it is characterized in that: the concrete steps of described step a are: the electrolytic aluminum liquation is delivered to smelting furnace, add the aluminium ingot that accounts for electrolytic aluminum liquation gross weight 20～40%, the control melt temperature is 750～780 ℃, and the mass percent of adjusting each elemental composition in the melt is: Si:0.1～0.15%, Fe:0.45～0.5%, Cu:0.1～0.15%, Mn:1.1～1.2%, Ti:0.02～0.04%, surplus are Al; Adopt pure nitrogen gas or pure argon to spray the refining agent refining in melt, stir, refining time is 8～10 minutes, leaves standstill then 15～25 minutes, removes the scum silica frost on aluminium liquid surface, pours into and leaves standstill in the stove, and it is 750～760 ℃ that the interior temperature of stove is left standstill in control; The aluminium liquid that leaves standstill in the stove is sent in the chute, and reverse adding aluminium titanium boron wire carries out grain refining, with pure nitrogen gas or pure argon aluminium liquid is carried out degassing processing then in degasification tank, adopts floamed ceramics filtrating piece that aluminium liquid is carried out filtration, purification after the degasification and handles; Aluminium liquid after the purification send the casting and rolling machine casting, and casting goes out the blank that thickness is 6.5～8.5mm.
4, the manufacture method of 3003 brand cathode aluminum foils as claimed in claim 3 is characterized in that: the add-on of described aluminium titanium boron wire adds 2～3 ‰ of preceding aluminium liquid weight for it.
5, as the manufacture method of claim 3 or 4 described 3003 brand cathode aluminum foils, it is characterized in that: the rotating speed of graphite rotator is 120～180r/min in the described degasification tank.
6, the manufacture method of 3003 brand cathode aluminum foils as claimed in claim 5 is characterized in that: described refining agent is injection refining agent SY-PJ1, and add-on is for adjusting 0.1～0.4% of melt weight after the elemental composition.
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