CN111195657A - Electronic aluminum foil composite material and electronic aluminum foil prepared from same - Google Patents
Electronic aluminum foil composite material and electronic aluminum foil prepared from same Download PDFInfo
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- CN111195657A CN111195657A CN202010027124.4A CN202010027124A CN111195657A CN 111195657 A CN111195657 A CN 111195657A CN 202010027124 A CN202010027124 A CN 202010027124A CN 111195657 A CN111195657 A CN 111195657A
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Abstract
The invention discloses an electronic aluminum foil composite material and an electronic aluminum foil prepared from the same. The electronic aluminum foil composite material comprises a substrate layer and functional layers arranged on the upper surface and the lower surface of the substrate layer; al in the substrate layer is more than 99.995 percent, Fe is less than 15ppm, Si is less than 15ppm, Cu is less than 10ppm, Zn is less than 5ppm, Ga is less than 5ppm, and the rest is less than 5 ppm; the functional layer contains more than 99.98% of Al, 10-25 ppm of Fe, 10-25 ppm of Si, 20-60 ppm of Cu, 15ppm of Zn, 15ppm of Ga and 0-2 ppm of Pb. The electronic aluminum foil prepared by the electronic aluminum foil composite material is relatively corrosion-resistant due to the substrate layer, and the problem of aluminum foil strength reduction caused by substrate layer corrosion is not considered when the whole electronic aluminum foil is corroded to increase the specific capacitance. The corrosion effect of the functional layers on the upper surface and the lower surface of the substrate layer can be fully adjusted, and the corrosion holes are guaranteed to be optimized. Therefore, the composite material electronic aluminum foil can not only ensure the optimization of corrosion, but also ensure the strength and mechanical property of the electronic aluminum foil, and effectively solve the contradiction between the increase of specific capacitance caused by the corrosion of the electronic aluminum foil and the strength of the electronic aluminum foil in the prior art.
Description
Technical Field
The invention belongs to the technical field of electronic materials. In particular to an electronic aluminum foil composite material and an electronic aluminum foil prepared by the same.
Background
The electronic aluminum foil is a key raw material of an aluminum electrolytic capacitor and is a basic material for manufacturing the electrode foil. Aluminum electrolytic capacitors are widely used in household appliances, computers, communication equipment, industrial control, electric automobiles, electric locomotives, and military and aerospace equipment. With the rapid development of electronic technology, the aluminum electrolytic capacitor is widely used, and is also widely applied in the environmental protection and energy saving fields of rail transit, flat panel display, solar energy, wind energy battery and the like, and the development of electronic aluminum foil is promoted more rapidly.
The performance of the electronic aluminum foil, which is used as a core material of the aluminum electrolytic capacitor, directly affects various use characteristics of the aluminum electrolytic capacitor. The capacitance of the electrolytic capacitor is the most important index of the performance, and at present, the corrosion technology is mostly adopted to form fluctuation on the surface of the aluminum foil to enlarge the surface area of the polar plate and greatly improve the specific capacitance, so the capacitance of the aluminum electrolytic capacitor is mainly influenced by the surface area of the aluminum foil after the corrosion of the electronic foil.
The corrosion of the conventional electronic aluminum foil is shown in fig. 1, and the electronic aluminum foil is integrally formed from the same material. Holes are formed on the upper surface and the lower surface of the aluminum foil after corrosion to increase the surface area, the middle part is the rest part after corrosion and is used as a matrix, and the total matrix ensures the strength and the mechanical property of the aluminum foil. In the actual etching process, in order to increase the capacitance, the upper surface and the lower surface of the aluminum foil need to be etched as much as possible to increase the surface area, but the strength of the electronic aluminum foil needs to be ensured, and the etching degree is difficult to control. Particularly, when the upper and lower surfaces of the whole electronic aluminum foil are corroded, the local corrosion performance is different, so that some corrosion holes are deep and some corrosion holes are shallow, and when the deep holes penetrate through the middle part, the shallow corrosion depth is small, so that the strength of the electronic aluminum foil cannot be ensured, and the best corrosion effect (corrosion to the maximum degree) cannot be ensured. And the probability of scrapping of the product is higher, which causes the waste of resources. Therefore, the specific capacitance and the strength and mechanical properties after corrosion become unbalanced spearheads in the corrosion process.
Disclosure of Invention
The invention aims at the technical problems that: in the prior art, the electronic aluminum foil is integrally formed and made of the same material. In the process of increasing the surface area and improving the capacitance by corrosion, the specific capacitance and the strength mechanical property of the electronic aluminum foil cannot be simultaneously met due to different local corrosion properties, the specific capacitance and the strength mechanical property are difficult to simultaneously meet the requirements, the product rejection rate is high, and the waste of aluminum resources is completed.
In order to solve the problems, the invention provides an electronic aluminum foil composite material, an electronic aluminum foil prepared from the electronic aluminum foil composite material, and a preparation method of the electronic aluminum foil composite material. The electronic aluminum foil is formed by compounding the middle corrosion-resistant base body part and the electronic aluminum foil materials on the upper surface and the lower surface of the middle corrosion-resistant base body part, the middle base body can avoid corrosion, the mechanical property of the electronic aluminum foil is ensured, the corrosion areas of the electronic aluminum foil on the upper surface and the lower surface of the base body can be ensured to the maximum extent, and the contradiction between the specific capacitance and the mechanical property of the electronic aluminum foil in the corrosion process of the electronic aluminum foil is solved. And the composite material electronic aluminum foil has good overall performance.
The invention is realized by the following technical scheme
The invention provides an electronic aluminum foil composite material, which comprises a substrate layer and functional layers arranged on the upper surface and the lower surface of the substrate layer; al in the substrate layer is more than 99.995%, and Al in the functional layer is more than 99.98%.
The electronic aluminum foil composite material comprises the following elements in the matrix layer: fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, others <5ppm, and the balance Al; the substrate layer is a corrosion-resistant layer,
the content of each element in the functional layer is as follows: fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn 15ppm, Ga 15ppm, Pb 0-2 ppm, and the balance Al.
The thickness ratio of the substrate layer to the functional layers on the upper and lower surfaces of the substrate layer of the electronic aluminum foil composite material is (40-47.5%): (5-20%): (40% -47.5%).
The invention also provides an electronic aluminum foil prepared by adopting the electronic aluminum foil composite material.
Therefore, the electronic aluminum foil obtained by the invention is relatively corrosion-resistant because the substrate layer, and the problem of aluminum foil strength reduction caused by substrate layer corrosion is not considered when the specific capacitance is increased by corroding the whole electronic aluminum foil. The corrosion effect of the functional layers on the upper surface and the lower surface of the substrate layer can be fully adjusted, and the corrosion holes are guaranteed to be optimized. Therefore, the composite material electronic aluminum foil can not only ensure the optimization of corrosion, but also ensure the strength and mechanical property of the electronic aluminum foil, and effectively solve the contradiction between the increase of specific capacitance caused by the corrosion of the electronic aluminum foil and the strength of the electronic aluminum foil in the prior art.
The invention also provides a preparation method of the electronic aluminum foil, which comprises the following steps:
(1) preparing a substrate layer:
putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust the components to Fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm and the other <5 ppm; then, carrying out slag skimming, refining, degassing, standing, filtering, casting, double-sided milling, heating, hot rolling and surface cleaning (cleaning surface foreign matters) in sequence, and cleaning to obtain a substrate layer;
(2) preparation of the functional layer
Putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding an intermediate alloy to adjust components of Fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn 15ppm, Ga 15ppm and Pb 0-2 ppm; then, carrying out slag skimming, refining, degassing, standing, filtering, casting, double-sided milling, heating, hot rolling and surface cleaning (cleaning surface foreign matters) in sequence, and cleaning to obtain a functional layer;
(3) preparing the composite material electronic aluminum foil:
a: taking the substrate layer in the step (1) and the two functional layers prepared in the step (2); stacking the functional layer, the substrate layer and the functional layer from bottom to top in sequence to complete preliminary compounding;
b: b, placing the primary composite material in the step a into a heating furnace, heating furnace gas to 450-620 ℃, and preserving heat for 6-18 hours at the temperature;
c. b, heating and then carrying out thermal compound rolling, wherein the initial rolling temperature of the thermal compound rolling is 450-570 ℃, the secondary final rolling temperature is above 320 ℃, the final rolling temperature is 220-280 ℃, the thermal compound rolling is carried out until the thickness of a finished product is 4.5-7.5 nm, and the thermal compound rolling is finished to obtain a composite material roll blank;
d. c, cold foil rolling is carried out on the composite material coil blank in the step c: rolling the composite material coil blank for 7-9 passes, wherein the reduction rate of each pass is 35% -50%, and the thickness of the coil blank is rolled to be 0.13-0.16 mm; or rolling to the thickness of 0.065-0.120 mm;
e. and finishing after cold foil rolling, and finishing to obtain the composite material electronic aluminum foil.
The electronic aluminum foil preparation method comprises the steps of (1) and (2) smelting for 30-70 min at the temperature of 750-770 ℃; the refining is carried out for 20-50 min at the temperature of 750-770 ℃; the standing is to stand for 30-80 min at the temperature of 750-770 ℃; the temperature during casting is 710-740 ℃, and the casting speed is 50-70 mm/min; the milling amount of each of the two surfaces of the double-surface milling is 2-6 mm; the heating is carried out in a heating furnace to 500-600 ℃, and the temperature is kept for 3-7 hours at the temperature; the hot rolling is to perform cogging hot rolling at 510-550 ℃ to the required thickness for later use;
the hot compound rolling in the step c is specifically as follows: firstly, rolling the primary composite material for 1-3 passes, wherein the rolling reduction of each pass is 5-10 mm, and the rolling speed is 10-20 m/min; then, rolling for two passes, wherein the rolling reduction of each pass is 10-20 mm, and the rolling speed is 20-30 m/min; and rolling for 10-16 passes, wherein the rolling reduction of each pass is 25-35 mm, the rolling speed is 50-150 m/min, and the lubricating and cooling are carried out by adopting emulsion, the concentration of the emulsion is 3% -5%, and the pressure is 0.3 +/-0.05 MPa.
According to the preparation method of the electronic aluminum foil, the finishing is to roll the cold foil to a coil blank with the thickness of 0.065-0.120 mm for straightening, and then the composite electronic aluminum foil is obtained.
The preparation method of the electronic aluminum foil comprises the following steps:
rolling cold foil to a coil blank with the thickness of 0.065-0.120 mm, carrying out surface cleaning by using cleaning oil (40# or 60# cleaning oil) (the surface cleanliness after cleaning is measured by a brightness detector, and the L value is more than 90 ℃), and heating and drying by using steam, wherein the drying temperature is 120-150 ℃; cutting the dried material roll (cutting the material roll to a small roll with the standard width of 500mm and the weight of 250-500 Kg), annealing the material roll by using an air furnace, heating the furnace gas to 310-350 ℃ within 5-20 hours, preserving the heat for 10-20 hours at the temperature, cooling the material roll to 80-120 ℃ after preserving the heat, discharging the material roll, and controlling the tensile strength of the material roll to be 50-70 MPa and the surface water brushing value to be more than 3 grades.
The preparation method of the electronic aluminum foil comprises the following steps after the cold foil is rolled and before the cold foil is finished: rolling the cold foil to a coil blank with the thickness of 0.13-0.16 mm, carrying out intermediate annealing, keeping the temperature at 230-260 ℃ for 8-12 hours, cooling, discharging, and controlling the tensile strength of the annealed coil blank to be 75-90 MPa and the yield strength to be 40-60 MPa; and (3) carrying out 1-pass rolling on the finished product after annealing, wherein the reduction rate is 15-22%, and the rolling speed is less than 200 m/min.
The preparation method of the electronic aluminum foil comprises the following steps:
cleaning the surface of a rolled coil blank by using cleaning oil (40# or 60# cleaning oil), heating and drying by using steam, wherein the temperature during drying is 120-150 ℃ (the surface cleanliness after cleaning is measured by using a brightness detector, and the L value is more than 9.); cutting the dried material roll (to a small roll with the standard width of 500mm and the weight of 250-500 Kg), and annealing by adopting vacuum protective gas (the protective gas is argon with the concentration of 99.999%): placing the cut material roll in an annealing furnace, vacuumizing to below 1Pa, filling argon until the pressure is 0.5-0.85 MPa, then heating the furnace gas to 400-500 ℃ within 5-10 hours, and preserving the heat for 5-10 hours at the temperature; and after heat preservation is finished, vacuumizing to below 20Pa, filling argon to 0.5-0.85 MPa, heating the temperature of furnace gas from 400-500 ℃ to 550-620 ℃ within 5-10 hours under the pressure condition, preserving heat for 5-15 hours at the temperature, and after heat preservation is finished, rolling materials, cooling to 150-250 ℃, and discharging.
The method ensures that the prepared composite material electronic aluminum foil has good performance through exploration and control, and completely meets the requirements of practical application. Meanwhile, the contradiction between the increase of specific capacitance due to corrosion and the strength of the electronic aluminum foil in the prior art is effectively solved.
Compared with the prior art, the invention has the following positive beneficial effects
The electronic aluminum foil prepared by the invention is formed by compounding the substrate layer and the functional layer, and the middle substrate layer is not easy to corrode, so that the functional layers on the upper surface and the lower surface of the middle substrate layer can be fully corroded, the corrosion problem of the middle substrate layer is not considered, the corrosion area of the functional layer can be increased to the greatest extent, the strength and the mechanical property of the electronic aluminum foil are ensured, and the contradiction between the strength and the specific capacitance of the electronic aluminum foil after corrosion is effectively solved;
when the electronic aluminum foil prepared by the invention is corroded to increase the specific capacitance, the corrosion effect can be fully adjusted, the optimization of corrosion holes is ensured, and the aims of improving the capacitance and the overall quality are achieved;
according to the preparation method, the matrix layer and the functional layer are compositely rolled through the research and control of the preparation process, and the preparation process fully ensures the properties of the composite material such as tensile strength, yield strength and the like, so that the prepared electronic aluminum foil completely meets the actual application requirements and can achieve a better effect;
the electronic aluminum foil can optimize the application range of products with various specifications, and the strength and the mechanical property of the electronic aluminum foil are fully guaranteed, so that the winding diameter and the number of turns can be flexibly increased or decreased according to the requirements of a capacitor.
Drawings
FIG. 1 is a schematic structural diagram of an electronic aluminum foil in the prior art,
fig. 2 is a schematic structural view of the composite electronic aluminum foil prepared by the present invention.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments for understanding the technical solutions of the present invention, but the present invention is not limited to the scope of the present invention.
Example 1
This example produced a hard low pressure aluminum foil.
An electronic aluminum foil composite material comprises a substrate layer and functional layers arranged on the upper surface and the lower surface of the substrate layer; al in the substrate layer is more than 99.995%, and Al in the functional layer is more than 99.98%.
Wherein the content of each element in the matrix layer is as follows: fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, others <5ppm, and the balance Al; the substrate layer is a corrosion-resistant layer. The content of each element in the functional layer is as follows: fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn <15ppm, Ga <15ppm, Pb 0ppm, and the balance of Al. The functional layer may be an aluminum alloy for electronic aluminum foil, which is well known in the art.
Wherein, the thickness proportion of the substrate layer and the functional layers on the upper and lower surfaces thereof is 40%: 20%: 40 percent, the total thickness of the composite material is 300mm, wherein the thickness of the substrate layer is 60mm, and the thickness of the two functional layers is 120 mm.
The preparation method of the electronic aluminum foil comprises the following steps:
(1) preparing a substrate layer:
putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust the components to Fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, the other <5ppm and the balance of Al; then, carrying out slag skimming, refining, degassing (introducing argon-chlorine mixed gas for degassing), standing, filtering, casting, double-sided milling, heating, hot rolling and surface cleaning (cleaning surface foreign matters) in sequence, and cleaning to obtain a substrate layer;
wherein the smelting is carried out for 40min at the temperature of 750-770 ℃;
refining for 30min at 750-770 ℃;
standing for 50min at the temperature of 750-770 ℃;
the temperature is 710-740 ℃ during casting (the cooling water flow is 1400l/min), and the casting speed is 60 mm/min;
the milling amount of each of the two surfaces of the double-surface milling is 3 mm;
the heating is carried out in a heating furnace to 550 +/-10 ℃, and the temperature is kept for 5 +/-0.5 hours at the temperature;
the hot rolling is cogging hot rolling at 510-550 ℃ until the thickness is 60mm, and a plurality of blocks are prepared for later use;
(2) preparation of the functional layer
Putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust components of Fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn <15ppm, Ga <15ppm, Pb 0ppm and the balance of Al; then, sequentially carrying out slagging-off, refining, degassing (argon-chlorine mixed gas is introduced for degassing during refining), standing, filtering, casting, double-sided milling, heating, hot rolling and surface cleaning (surface foreign matter cleaning), and cleaning to obtain a functional layer;
wherein the smelting is carried out for 40min at the temperature of 750-770 ℃;
refining for 30min at 750-770 ℃;
standing for 50min at the temperature of 750-770 ℃;
the temperature is 710-740 ℃ during casting (the cooling water flow is 1400l/min), and the casting speed is 60 mm/min;
the milling amount of each of the two surfaces of the double-surface milling is 3 mm;
the heating is carried out in a heating furnace to 550 +/-10 ℃, and the temperature is kept for 5 +/-0.5 hours at the temperature;
the hot rolling is cogging hot rolling at 510-550 ℃ until the thickness is 120mm, and a plurality of blocks are prepared for later use;
(3) preparing the composite material electronic aluminum foil:
a: taking the substrate layer in the step (1) and the two functional layers prepared in the step (2); the functional layer, the base layer and the functional layer are sequentially stacked from bottom to top and can be bound and fixed by three steel bars (removed before hot compounding rolling) to finish primary compounding;
b: b, placing the stacked composite material in the step a into a heating furnace, heating the furnace gas to 550 +/-10 ℃, and preserving the heat for 10 hours at the temperature;
c. b, heating and then carrying out hot compound rolling, wherein the initial rolling temperature of the hot compound rolling is 530-550 ℃, the secondary final rolling temperature is above 320 ℃, the final rolling temperature is 220-280 ℃, the hot compound rolling is carried out until the thickness of a finished product is 5.5mm, and the hot compound rolling is finished to obtain a composite material coil blank;
the hot composite rolling is as follows: firstly, removing the three bundled and fixed steel bars, and then rolling the primary composite material for 2 passes, wherein the rolling reduction of each pass is 7mm, and the rolling speed is 15 m/min; then, two passes of rolling are carried out, the reduction of each pass is 15mm, and the rolling speed is 25 m/min; rolling for 13 passes, wherein the rolling reduction of each pass is 25-35 mm, the rolling speed is 100-140 m/min, the emulsion is adopted for lubrication and cooling during rolling, the concentration of the emulsion is 3% -5%, and the pressure is 0.3 +/-0.05 MPa;
d. c, cold foil rolling is carried out on the composite material coil blank in the step c: rolling the composite material coil blank by 8 passes to obtain a finished product of low-pressure foil with the thickness of 0.100 mm;
e. after cold foil rolling, straightening and withdrawing according to the plate shape condition to ensure that the plate shape meets the requirements; and cutting the steel wire into small rolls with the standard width of 500mm and the weight of 250-500 Kg according to the required weight, and packaging and warehousing after the corrosion rate is detected to be qualified (less than 0.2%).
Example 2
This example produced a soft low pressure aluminum foil.
An electronic aluminum foil composite material comprises a substrate layer and functional layers arranged on the upper surface and the lower surface of the substrate layer; al in the substrate layer is more than 99.995%, and Al in the functional layer is more than 99.98%.
Wherein the content of each element in the matrix layer is as follows: fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, others <5ppm, and the balance Al; the substrate layer is a corrosion-resistant layer. The content of each element in the functional layer is as follows: fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn <15ppm, Ga <15ppm, Pb 0ppm, and the balance of Al. The functional layer is an aluminum alloy for electronic aluminum foil well known in the art.
Wherein, the thickness proportion of the substrate layer and the functional layers on the upper and lower surfaces thereof is 40%: 20%: 40 percent, the total thickness of the composite material is 300mm, wherein the thickness of the substrate layer is 60mm, and the thickness of the two functional layers is 120 mm.
The preparation method of the electronic aluminum foil comprises the following steps:
(1) preparing a substrate layer:
putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust the components to Fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, the other <5ppm and the balance of Al; then, carrying out slag skimming, refining, degassing (argon-chlorine mixed gas is introduced for degassing during refining), standing, filtering, casting, double-sided milling, heating, hot rolling, surface cleaning (surface foreign matter cleaning), and cleaning to obtain a substrate layer;
wherein the smelting is carried out for 40min at the temperature of 750-770 ℃;
refining for 30min at 750-770 ℃;
standing for 50min at the temperature of 750-770 ℃;
the temperature is 710-740 ℃ during casting (the cooling water flow is 1400l/min), and the casting speed is 60 mm/min;
the milling amount of each of the two surfaces of the double-surface milling is 3 mm;
the heating is carried out in a heating furnace to 550 +/-10 ℃, and the temperature is kept for 5 +/-0.5 hours at the temperature;
the hot rolling is cogging hot rolling at 510-550 ℃ to 60mm in thickness, and a plurality of blocks are prepared for later use;
(2) preparation of the functional layer
Putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust components of Fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn <15ppm, Ga <15ppm, Pb 0ppm and the balance of Al; then, sequentially carrying out slagging-off, refining, degassing (argon-chlorine mixed gas is introduced for degassing during refining), standing, filtering, casting, double-sided milling, heating, hot rolling and surface cleaning (surface foreign matter cleaning), and cleaning to obtain a functional layer;
wherein the smelting is carried out for 40min at the temperature of 750-770 ℃;
refining for 30min at 750-770 ℃;
standing for 50min at the temperature of 750-770 ℃;
the temperature is 710-740 ℃ during casting (the cooling water flow is 1400l/min), and the casting speed is 60 mm/min;
the milling amount of each of the two surfaces of the double-surface milling is 3 mm;
the heating is carried out in a heating furnace to 550 +/-10 ℃, and the temperature is kept for 5 +/-0.5 hours at the temperature;
the hot rolling is cogging hot rolling at 510-550 ℃ to 120mm thick, and a plurality of blocks are prepared for later use;
(3) preparing the composite material electronic aluminum foil:
a: taking the substrate layer in the step (1) and the two functional layers prepared in the step (2); stacking the functional layer, the substrate layer and the functional layer from bottom to top in sequence to complete preliminary compounding;
b: b, placing the primary composite material in the step a into a heating furnace, heating the furnace gas to 550 +/-10 ℃, and preserving heat for 12 hours at the temperature;
c. b, heating and then carrying out hot compound rolling, wherein the initial rolling temperature of the hot compound rolling is 540 +/-10 ℃, the secondary final rolling temperature is above 320 ℃, the final rolling temperature is 220-280 ℃, the hot compound rolling is carried out until the thickness of a finished product is 5.5mm, and the hot compound rolling is finished to obtain a composite material coil blank;
the hot compound rolling is as follows: firstly, rolling the primary composite material for 2 passes, wherein the rolling reduction of each pass is 6mm, and the rolling speed is 15 m/min; then, rolling for two passes is carried out, the rolling reduction of each pass is 15mm, and the rolling speed is 20-30 m/min; rolling for 13 passes, wherein the rolling reduction of each pass is 25-35 mm, the rolling speed is 50-150 m/min, and the rolling is lubricated and cooled by adopting emulsion, the concentration of the emulsion is 3-5%, and the pressure is 0.3 +/-0.05 MPa;
d. c, cold foil rolling is carried out on the composite material coil blank in the step c: rolling the composite material coil blank by 8 passes, wherein the reduction rate of each pass is 35-50%, and the thickness of a finished product coil is 0.100 mm;
e. c, rolling the cold foil in the step d to a coil blank with the thickness of 0.100mm, carrying out surface cleaning by using cleaning oil (40# or 60# cleaning oil) (the surface cleanliness after cleaning is measured by using a brightness detector, and the L value is more than 90 ℃), and heating and drying by using steam, wherein the temperature during drying is 120-150 ℃;
and cutting the dried material into small rolls with the standard width of 500mm and the weight of 250-500 Kg, annealing the small rolls by using an air furnace, placing the cut rolls into the air furnace, heating the furnace gas to 320 ℃ within 10 hours, preserving the heat for 15 hours at the temperature, cooling the rolls to the temperature below 100 ℃ after heat preservation, discharging the rolls out of the furnace, controlling the tensile strength of the rolls to be 50-70 MPa, controlling the surface water brushing value to be more than 3 grades, and warehousing the rolls after the rolls are qualified.
Example 3
This example prepared a high pressure aluminum foil.
An electronic aluminum foil composite material comprises a substrate layer and functional layers arranged on the upper surface and the lower surface of the substrate layer; al in the substrate layer is more than 99.995%, and Al in the functional layer is more than 99.98%.
Wherein the content of each element in the matrix layer is as follows: fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, others <5ppm, and the balance Al; the substrate layer is a corrosion-resistant layer. The content of each element in the functional layer is as follows: fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn 15ppm, Ga 15ppm, Pb 0.5-2 ppm. The functional layer may be an aluminum alloy for electronic aluminum foil, which is well known in the art.
Wherein, the thickness proportion of the substrate layer and the functional layers on the upper and lower surfaces thereof is 40%: 20%: 40 percent, the total thickness of the composite material is 300mm, wherein the thickness of the substrate layer is 60mm, and the thickness of the two functional layers is 120 mm.
The preparation method of the electronic aluminum foil comprises the following steps:
(1) preparing a substrate layer:
putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust the components to Fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, the other <5ppm and the balance of Al; then, carrying out slag skimming, refining, degassing (argon-chlorine mixed gas is introduced for degassing during refining), standing, filtering, casting, double-sided milling, heating, hot rolling, surface cleaning (surface foreign matter cleaning), and cleaning to obtain a substrate layer;
wherein the smelting is carried out for 40min at the temperature of 750-770 ℃;
refining for 30min at 750-770 ℃;
standing for 50min at the temperature of 750-770 ℃;
the temperature is 710-740 ℃ during casting (the cooling water flow is 1400l/min), and the casting speed is 60 mm/min;
the milling amount of each of the two surfaces of the double-surface milling is 3 mm;
the heating is carried out in a heating furnace to 550 +/-10 ℃, and the temperature is kept for 5 +/-0.5 hours at the temperature;
the hot rolling is cogging hot rolling at 510-550 ℃ until the thickness is 60mm, and a plurality of blocks are prepared for later use;
(2) preparation of the functional layer
Putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust components of Fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn 15ppm, Ga 15ppm and Pb 0.5-2 ppm; then, carrying out slag skimming, refining, degassing (argon-chlorine mixed gas is introduced for degassing during refining), standing, filtering (operation well known by the technical personnel in the field), casting, double-sided milling, heating, hot rolling, surface cleaning (surface foreign matter cleaning), and cleaning to obtain a functional layer;
wherein the smelting is carried out for 40min at the temperature of 750-770 ℃;
refining for 30min at 750-770 ℃;
standing for 50min at the temperature of 750-770 ℃;
the temperature is 710-740 ℃ during casting (the cooling water flow is 1400l/min), and the casting speed is 60 mm/min;
the milling amount of each of the two surfaces of the double-surface milling is 3 mm;
the heating is carried out in a heating furnace to 550 +/-10 ℃, and the temperature is kept for 5 +/-0.5 hours at the temperature;
the hot rolling is cogging hot rolling at 510-550 ℃ to 120mm thick, and a plurality of blocks are prepared for later use;
(3) preparing the composite material electronic aluminum foil:
a: taking the substrate layer in the step (1) and the two functional layers prepared in the step (2); the functional layer, the base layer and the functional layer are sequentially stacked from bottom to top and can be bound and fixed by three steel bars (removed before hot compounding rolling) to finish primary compounding;
b: b, placing the primary composite material in the step a into a heating furnace, heating the furnace gas to 560 +/-10 ℃, and preserving the heat for 13 hours at the temperature;
c. b, heating and then carrying out thermal compound rolling, wherein the initial rolling temperature of the thermal compound rolling is 550 +/-10 ℃, the secondary final rolling temperature is above 320 ℃, the final rolling temperature is 220-280 ℃, the thermal compound rolling is carried out until the thickness of a finished product is 6mm, and the thermal compound rolling is finished to obtain a composite material coil blank;
the hot compound rolling is as follows: firstly, removing the three bundled and fixed steel bars, and then rolling the primary composite material for 2 passes, wherein the rolling reduction of each pass is 6mm, and the rolling speed is 15 m/min; then rolling for 2 passes is carried out, the reduction of each pass is 15mm, and the rolling speed is 25 m/min; rolling for 13 passes, wherein the rolling reduction of each pass is 25-35 mm, the rolling speed is 90-150 m/min, and the rolling is lubricated and cooled by adopting emulsion, the concentration of the emulsion is 3-5%, and the pressure is 0.3 +/-0.05 MPa;
d. c, cold foil rolling is carried out on the composite material coil blank in the step c: rolling the composite material coil blank by 9 passes, wherein the reduction rate of each pass is 35-50%, and the thickness of the coil blank is rolled to be 0.157 mm;
e. c, rolling the cold foil in the step d to a coil blank with the thickness of 0.157mm, carrying out intermediate annealing, placing the coil blank in an annealing furnace, keeping the temperature for 10 hours at the furnace gas temperature of 230-260 ℃, cooling and discharging, wherein the tensile strength of the annealed coil blank is 75-90 MPa, and the yield strength is 40-60 MPa;
f. e, rolling the coil blank subjected to intermediate annealing in the step e for 1 finished product pass, wherein the reduction rate of the pass is 20%, the thickness of the finished product is 0.126mm, and the rolling speed is less than 200 m/min;
g. f, cleaning the surface of the rolled coil blank of the finished product in the step f by using cleaning oil (40# or 60# cleaning oil), heating and drying by using steam, wherein the temperature during drying is 120-150 ℃ (the surface cleanliness after cleaning is more than 9 ℃ measured by a brightness detector);
h. and g, cutting the material roll dried in the step g into a small roll with the standard width of 500mm and the weight of 250-500 Kg, and annealing the small roll in an annealing furnace by using vacuum protective gas (the protective gas is 99.999 percent of argon): firstly, placing a sheared material in an annealing furnace, vacuumizing to below 1Pa, filling argon until the pressure is 0.65MPa, heating the temperature of furnace gas to 450 ℃ within 5 hours under the pressure condition, and preserving the heat for 8 hours at the temperature; and after the heat preservation is finished, vacuumizing the annealing furnace to below 20Pa, filling argon to 0.8MPa, raising the temperature of furnace gas from 450 ℃ to 600 ℃ within 5 hours under the pressure condition, preserving the heat at the temperature for 10 hours, cooling the material coil to below 200 ℃ after the heat preservation is finished, and discharging.
And detecting that the cube texture of the prepared high-pressure aluminum foil is more than 95%, the pressure resistance value of the surface oxide film is less than 1.5, and warehousing the high-pressure aluminum foil after the L value of the brightness detection is qualified.
Claims (10)
1. The electronic aluminum foil composite material is characterized by comprising a substrate layer and functional layers arranged on the upper surface and the lower surface of the substrate layer; al in the substrate layer is more than 99.995%, and Al in the functional layer is more than 99.98%.
2. The electronic aluminum foil composite material as claimed in claim 1,
the content of each element in the substrate layer is as follows: fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, others <5ppm, and the balance Al;
the content of each element in the functional layer is as follows: fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn 15ppm, Ga 15ppm, Pb 0-2 ppm, and the balance Al.
3. The electronic aluminum foil composite material as claimed in claim 1 or 2, wherein the thickness ratio of the substrate layer to the functional layers on the upper and lower surfaces thereof is (40% to 47.5%): (5-20%): (40% -47.5%).
4. An electronic aluminum foil prepared from the electronic aluminum foil composite material as claimed in any one of claims 1 to 3.
5. A method for preparing the electronic aluminum foil of claim 4, which comprises the following steps:
(1) preparing a substrate layer:
putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding a master alloy to adjust the components to Fe <15ppm, Si <15ppm, Cu <10ppm, Zn <5ppm, Ga <5ppm, the other <5ppm and the balance of Al; then carrying out slag skimming, refining, degassing, standing, filtering, casting, double-sided milling, heating, hot rolling, surface cleaning and cleaning in sequence to obtain a substrate layer;
(2) preparation of the functional layer
Putting an aluminum ingot into a melting furnace, sequentially carrying out melting stirring, sampling analysis and adding an intermediate alloy to adjust components of Fe 10-25 ppm, Si 10-25 ppm, Cu 20-60 ppm, Zn 15ppm, Ga 15ppm, Pb 0-2 ppm and the balance of Al; then, sequentially carrying out slagging-off, refining, degassing, standing, filtering, casting, double-sided surface milling, heating, hot rolling, surface cleaning and cleaning to obtain a functional layer;
(3) preparing the composite material electronic aluminum foil:
a: taking the substrate layer in the step (1) and the two functional layers prepared in the step (2); stacking the functional layer, the substrate layer and the functional layer from bottom to top in sequence to complete preliminary compounding;
b: b, placing the primary composite material in the step a into a heating furnace, heating to the furnace gas temperature of 450-620 ℃, and preserving heat for 6-18 hours at the temperature;
c. b, heating and then carrying out thermal compound rolling, wherein the initial rolling temperature of the thermal compound rolling is 450-570 ℃, the secondary final rolling temperature is above 320 ℃, the final rolling temperature is 220-280 ℃, the thermal compound rolling is carried out until the thickness of a finished product is 4.5-7.5 mm, and the thermal compound rolling is finished to obtain a composite material roll blank;
d. c, cold foil rolling is carried out on the composite material coil blank in the step c: rolling the composite material coil blank for 7-9 passes, wherein the reduction rate of each pass is 35% -50%, and the thickness of the coil blank is rolled to be 0.13-0.16 mm; or rolling to the thickness of 0.065-0.120 mm;
e. and finishing after cold foil rolling, and finishing to obtain the composite material electronic aluminum foil.
6. The method of manufacturing electronic aluminum foil according to claim 5,
the smelting in the step (1) and the step (2) is carried out for 30-70 min at the temperature of 750-770 ℃; the refining is carried out for 20-50 min at the temperature of 750-770 ℃; the standing is to stand for 30-80 min at the temperature of 750-770 ℃; the temperature during casting is 710-740 ℃, and the casting speed is 50-70 mm/min; the milling amount of each of the two surfaces of the double-surface milling is 2-6 mm; the heating is carried out in a heating furnace to 500-600 ℃, and the temperature is kept for 3-7 hours at the temperature; the hot rolling is to perform cogging hot rolling at 510-550 ℃ to the required thickness for later use;
the hot compound rolling in the step c is specifically as follows: firstly, rolling the primary composite material for 1-3 passes, wherein the rolling reduction of each pass is 5-10 mm, and the rolling speed is 10-20 m/min; then, rolling for two passes, wherein the rolling reduction of each pass is 10-20 mm, and the rolling speed is 20-30 m/min; and rolling for 10-16 passes, wherein the rolling reduction of each pass is 25-35 mm, the rolling speed is 50-150 m/min, and the lubricating and cooling are carried out by adopting emulsion, the concentration of the emulsion is 3% -5%, and the pressure is 0.3 +/-0.05 MPa.
7. The preparation method of the electronic aluminum foil as claimed in claim 5, wherein the finishing is cold foil rolling to a coil blank with a thickness of 0.065-0.120 mm, and performing straightening and withdrawing to obtain the composite electronic aluminum foil.
8. The method of manufacturing electronic aluminum foil as claimed in claim 5, wherein the finishing comprises the steps of:
rolling the cold foil to a coil blank with the thickness of 0.065-0.120 mm, and cleaning the surface of the coil blank by using cleaning oil, and heating and drying by using steam, wherein the temperature during drying is 120-150 ℃;
cutting the dried material roll, annealing by using an air furnace, heating the furnace gas to 310-350 ℃ within 5-20 hours, preserving the heat for 10-20 hours at the temperature, cooling to 80-120 ℃ after preserving the heat, and discharging.
9. The method for preparing electronic aluminum foil according to claim 5, wherein the step e further comprises the following steps after cold foil rolling and before finishing:
carrying out intermediate annealing on the rolled blank with the thickness of 0.13-0.16 mm after cold foil rolling, preserving the heat for 8-12 hours at the temperature of 230-260 ℃, and cooling and discharging;
and (3) carrying out 1-pass rolling on the finished product after annealing, wherein the reduction rate is 15-22%, and the rolling speed is less than 200 m/min.
10. The method of manufacturing electronic aluminum foil as claimed in claim 9, wherein the finishing step comprises the steps of:
cleaning the surface of a rolled coil blank by using cleaning oil, and heating and drying by using steam, wherein the temperature during drying is 120-150 ℃;
cutting the dried material roll, and then annealing by adopting vacuum protective gas: putting the cut material roll into an annealing furnace, vacuumizing to below 1Pa, filling argon until the pressure is 0.5-0.85 MPa, then heating the furnace gas from 120-150 ℃ to 400-500 ℃ within 5-10 hours, and preserving the heat for 5-10 hours at the temperature; and after heat preservation is finished, vacuumizing to below 20Pa, filling argon to 0.5-0.85 MPa, heating the temperature of furnace gas from 400-500 ℃ to 550-620 ℃ within 5-10 hours under the pressure condition, preserving heat for 5-15 hours at the temperature, and after heat preservation is finished, rolling materials, cooling to 150-250 ℃, and discharging.
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