CN104505260B - A kind of method that mesohigh etched foil is prepared with pulse direct current superimposed current - Google Patents
A kind of method that mesohigh etched foil is prepared with pulse direct current superimposed current Download PDFInfo
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- CN104505260B CN104505260B CN201410728211.7A CN201410728211A CN104505260B CN 104505260 B CN104505260 B CN 104505260B CN 201410728211 A CN201410728211 A CN 201410728211A CN 104505260 B CN104505260 B CN 104505260B
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000011888 foil Substances 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 42
- 239000005030 aluminium foil Substances 0.000 claims abstract description 28
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000012805 post-processing Methods 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- -1 aluminum ions Chemical class 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 22
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000005530 etching Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 4
- 230000003044 adaptive effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 12
- 238000005452 bending Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 241000693079 Maloideae Species 0.000 description 1
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
The present invention relates to a kind of method that mesohigh etched foil is prepared with pulse direct current superimposed current, comprise the following steps：Previous treatment, the first two treatment, one-level hair engaging aperture, middle treatment, two grades of hair engaging aperture and post processing, methods described removes aluminium foil surface oxide-film by previous treatment with strong alkali solution, the first two treatment remains alkaline solution with strongly acidic solution with aluminium foil surface, one-level hair engaging aperture generates hole by the method for pulse direct current superimposed current, middle treatment further expands the radius and depth of hole by direct current, two grades of hair engaging aperture fall the aluminium ion that aluminium foil surface is remained by post-processing chemical erosion, whole technological process is simple, it is strong to corrosion tank liquor change adaptive, the corrosion hole uniform ground of generation, the electrostatic specific volume of etched foil is improved by a relatively large margin, there is more excellent mechanical performance simultaneously, solve the limitation that hair engaging aperture process in traditional etching process can not be powered off.
Description
Technical field
The present invention relates to the preparation field of mesohigh anodic attack paper tinsel, and in particular to one kind pulse direct current superimposed current system
The method of standby mesohigh etched foil.
Technical background
Traditional mesohigh anode foils use chromic acid corrosion system, advantage be due to chromic acid corrosive power in itself compared with
By force, therefore required electric current is smaller, there is greater advantage in terms of caloric value and static specific volume, but due to chromic acid system face
Face more serious environmental protection pressure, foreign countries stop using substantially, domestic enterprise is also actively eliminating central.
Current main flow etching process both domestic and external is generally the mixed acid system of sulfuric acid and hydrochloric acid, its typical process flow bag
Include pre-treatment → one-level hair engaging aperture → secondary chambering → post processing, the main purpose of pre-treatment be dispel light paper tinsel surface greasy dirt,
Oxide-film and partial impurities, the light paper tinsel surface for be more uniformly distributed, activating；First process is the key of whole etching process,
Reasonably combined nitration mixture ratio, coordinates the key parameters such as electric current, electricity and temperature, thus formed be evenly distributed, density reasonably just
Beginning hole, because first process has to last for power-up, therefore aluminium ion can not be excluded in time in result in hole, it is impossible to produce reason
The tunnel model hole thought, hole produces fold, and some perforations growth is turned to, and produces branch hole, and this is with regard to greatly drop
Low etched foil performance；Secondary chambering is then further to expand aperture and hole depth, will to corrosion hole according to different operating voltage
Ask different, using the 2-5 electrolytic cell of V, general aperture requirement is bigger, and Secondary process electrolysis time is more long for Secondary process, due to
Secondary process typically uses acid solution, and strong self-corrosion phenomenon, therefore two grades of mistakes can be produced in prolonged electrolytic process
Journey can typically produce it is more serious degrade phenomenon, so as to cause to be electrolysed, institute's subfam. Spiraeoideae increases and the mechanical performance of aluminium foil declines；
Last handling process is then aluminium residual in cleaning aluminium foil surface and hole, increases corrosion foil surface clearness.
The content of the invention
Summary of the invention
Defect and deficiency it is an object of the invention to overcome prior art, propose a kind of pulse direct current superimposed current system
The method of the etched foil of standby mesohigh anode foils, the method can solve that one-level hair engaging aperture process Hole is uneven, caloric value mistake
Big and secondary chambering process degrades the problems such as causing higher weight-loss ratio, mechanical performance and relatively low electrostatic specific volume.
In order to achieve the above object, technical scheme is corroded there is provided a kind of pulse direct current superimposed current mesohigh
The preparation method of paper tinsel, comprises the following steps：
A) previous treatment：Light paper tinsel raw material is put into the sodium hydroxide solution of 0.5-1mol/L, 60- is processed at 30-40 DEG C
120Sec；
B) the first two treatment：The above-mentioned aluminium foil by previous treatment is put into concentration for 1-5Wt% sulfuric acid and 10-20Wt% nitre
In sour mixed solution, 90-120Sec is processed at 55-70 DEG C；
C) one-level hair engaging aperture：Sulfuric acid, the 3- that concentration is 30-50Wt% will be put into by the aluminium foil after above-mentioned the first two treatment
In the hydrochloric acid of 5Wt%, the aluminum ions tank liquor of 1-2Wt%, 50-80Sec is electrolysed at 60-80 DEG C；
D) treatment in：To be put into 3-5%Wt% dilute phosphoric acid solutions by the aluminium foil of hair engaging aperture step process, at 55-65 DEG C
Treatment 120-180Sec；
E) two grades of hair engaging aperture：The aluminium foil that will be processed in process is put into nitric acid, the 0.2- that tank liquor composition proportion is 5-8Wt%
In the aluminium ion of 0.5Wt% and the calcium polystyreme sulphonate solution of 0.01-0.5Wt%, in 65-80 DEG C of direct current power-up treatment 12-
18min；
F) post-process：The aluminum ions solution of nitric acid containing 1-3Wt%, 0.5-3Wt% will be put into by the aluminium foil of two grades of hair engaging aperture
In, soak 3-4min at 60-70 DEG C；
G) dry：2-5min is processed by being put into 80-120 DEG C of air dry oven by the aluminium foil of post processing, after drying
Foil closing.
Detailed description of the invention
A kind of method for preparing pulse direct current superimposed current mesohigh etched foil that technology according to the present invention scheme is provided,
The complexity and uniformity of one-level hair engaging aperture process are directly connected to due to light paper tinsel surface oxidation film thickness and uniformity, therefore
Select suitable pre-treating technology extremely important.Pre-treatment is divided into two steps in the inventive solutions, previous treatment is
The process of alkalescence pretreatment is first carried out to high-purity aluminum foil：Concentration is 0.5-1mol/L, is added with the phosphide element of 60-90ppm
With the Ce elements sodium hydroxide solution of 20-40ppm, the oil on 60-120Sec removal light paper tinsels surface is processed at a temperature of 30-40 DEG C
Dirty, dissolving partial surface oxidation film, obtains the aluminium foil that surface is uniform, oxide-film is relatively thin；The first two treatment is using in acid solution
With the process of light paper tinsel remained on surface alkaline matter：Use 1-5Wt% sulfuric acid, 10-20Wt% nitric acid, in 55-70 DEG C of temperature strip
The alkaline matter of light paper tinsel remained on surface is neutralized under part after treatment 90-120Sec, aluminium foil surface oxide-film is acidified, is conducive in one-level
Equally distributed pitting point is formed before hair engaging aperture.
One-level hair engaging aperture is corroded：First process is the key of whole etching process, directly decide aperture density degree and
Whether even, traditional mesohigh etching process uses constant dc current chemical attack, and its shortcoming is on the one hand lasting big electricity
Stream can cause aluminium foil surface caloric value larger, so that easily there is deviation in the aspect such as etched foil outward appearance, capacity and buckling performance, separately
On the one hand lasting constant dc current also aluminium ion can not be discharged in time during causing corrosion so that the corrosion hole direction of growth
Generation deviates even steering, causes to corrode the useless branch hole increase of the inhomogeneities of hole longitudinal direction and horizontal direction, so that
Reduce etched foil performance.Therefore, present invention employs a kind of method of pulse direct current superimposed current corrosion, in a single group or
Many group pulses, positive dutycycle 50-80%, Mean Forward Current about 0.4-0.8A/cm2, applied on the basis of positive time 100ms
Plus one continue 5-15A perseverance direct currents, that is, ensureing to be realized on the basis of not powering off the alternating corrosion of current, so as to meet
In low current stage corrosion process aluminium foil surface, radiating and hole growth course aluminium ion are able to exchange in time in time.
Middle treatment：Because secondary chambering process typical time is more long, aluminium foil surface is produced in prolonged acid soak
Phenomenon is degraded, this can significantly reduce etched foil performance, therefore be put into the middle of 3-5Wt% dilute phosphoric acid solutions in middle process step,
120-180Sec is processed under 55-65 DEG C of temperature conditionss, contributes to surface to form phosphate radical passivating film, so as in secondary chambering
During, the depth that more electricity are used for hole grows, and less aluminium foil surface degrades while reducing energy consumption.
According to the method for preparing mesohigh etched foil that above-mentioned technical proposal is provided, light paper tinsel raw material are by high-temperature vacuum
Stepped annelaing treatment, thickness are 110-130 μm, the high-purity aluminum foil of cubic texture >=92%.
According to above-mentioned technical proposal provide the method for preparing mesohigh etched foil, purity >=99.98% of light paper tinsel raw material,
The content of wherein impurity element Pb, Zn, Mg, Cu, Fe and Si is respectively 0-1.0ppm, 2-3ppm, 3-7ppm, 40-70ppm, 5-
15ppm、5-25ppm。
According to the method for preparing mesohigh etched foil that above-mentioned technical proposal is provided, it is added with the treatment fluid of previous treatment
Phosphide element and Ce elements, its content are respectively 60-90ppm and 20-40ppm.
According to the method for preparing mesohigh etched foil that above-mentioned technical proposal is provided, one-level hair engaging aperture applies electric current for direct current
The superimposed current of pulse.
According to the method for preparing mesohigh etched foil that above-mentioned technical proposal is provided, superimposed current is in the small direct currents of 10-20A
Increase a single group or many group pulses on the basis of electricity, wherein positive dutycycle is 50-80%, Mean Forward Current is 0.4-
0.8A/cm2, the positive time is 100ms.
According to the method for preparing mesohigh etched foil that above-mentioned technical proposal is provided, using 3-4 during two grades of hair engaging aperture
Electrolytic cell, adds the calcium polystyreme sulphonate of 0.01-0.03Wt%, current density 0.05-0.1A/cm in tank liquor composition2。
According to the method for preparing mesohigh etched foil that above-mentioned technical proposal is provided, post processing is using containing aluminum ions nitric acid
Weak solution, concentration of nitric acid is 1-2Wt%, and aluminium ion concentration is 1-2Wt%.
Unless explicitly stated otherwise in contrast, otherwise, all scopes that the present invention is quoted include end value.For example, " forward direction is flat
Equal electric current is 0.4-0.8A/cm2" represent Mean Forward Current scope be 0.4≤I≤0.8A/cm2Scope be 1.5≤W≤
3.0。
The beneficial effects of the present invention are：
1) pretreatment process is divided into two by the preparation method that the present invention is provided on traditional sulfur process process base
Section, alkali process and acid treatment, have used the power-up forms of corrosion of pulse direct current superimposed current, at two grades during one-level hair engaging aperture
It is passivated using phosphoric acid,diluted overlay film before reaming, is used containing aluminum ions nitric acid weak solution, the whole work of the method in post-processing stages
Skill flow is simple, strong to corrosion tank liquor change adaptive, and the corrosion hole uniform ground of generation improves etched foil by a relatively large margin
Electrostatic specific volume, while there is more excellent mechanical performance, what the hair engaging aperture process in traditional etching process that solves can not be powered off
Limitation.
2) previous treatment dispels light paper tinsel surface and oil contaminant using alkaline solution, dissolves surface film oxide, and acquisition surface is uniform, oxygen
Change the relatively thin aluminium foil of film；
3) intermediate pressure section 240Vf specific volumes level can reach 2.5 μ F/cm2, 5-8%, pulling force 20-25N/ are higher by than conventional flat
Cm, meets following process demand；High-pressure side 600Vf specific volumes level is in 0.64 μ F/cm2, 3-6%, pulling force are higher by than conventional flat
22-26N/cm, meets following process demand；And in product appearance, due to caloric value reduction, useless branch hole and on-uniform porosity
Deep to reduce, the aberrations in property such as product appearance and specific volume is less, and production stability rises, and greatly improves traditional etching process
The limitation that middle hair engaging aperture process can not be powered off.
Brief description of the drawings
Fig. 1 is the current diagram in the embodiment of the present invention 1.
Fig. 2 is the current diagram in the embodiment of the present invention 2.
Fig. 3 is the current diagram in the embodiment of the present invention 3.
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that for a person skilled in the art on the basis of this innovation and creation design, some deformations for making and
Improve, belong to protection scope of the present invention.Raw material used can be obtained by commercial sources in embodiment.Using industry
Current standard is tested, specific as follows：
Embodiment 1
From the thickness light paper tinsel of Ruyuan Dongyangguang Fine Foil Co., Ltd. LC models 115, its basic element be configured to Al >=
99.99%, other element species and its content are Pb 0-1.0ppm, Zn 2-3ppm, Mg 3-7ppm, Cu 40-70ppm, Fe
5-15ppm、Si 5-25ppm；Through high-temperature vacuum stepped annelaing, make its cubic texture >=95%；The 1mol/L hydroxides at 35 DEG C
90Sec is soaked in sodium solution；It is put into after washing in the nitration mixture of 3Wt% sulfuric acid and 10Wt% nitric acid composition, in 60 DEG C of temperature strip
120Sec is processed under part；Carry out one-level hair engaging aperture after washing, electric current is in a single group square-wave pulse, positive dutycycle 60%, just
To average current about 0.5A/cm2, apply one on the basis of positive time 100ms and continue 10A perseverance direct currents, its current diagram
See accompanying drawing 1, corrosion 65Sec is powered up at a temperature of 75 DEG C；It is put into after washing in 5Wt% dilute phosphoric acid solutions, at a temperature of 60 DEG C
Treatment 120Sec；Paillon foil is put into second-level groove, tank liquor composition proportion is the nitric acid of 6Wt%, 0.2% aluminium ion and
The calcium polystyreme sulphonate of 0.01Wt%, using 2 electrolytic cells of V, in current density 0.1A/cm2, under conditions of 65 DEG C of temperature
Electrochemical corrosion 8min (i.e. each V processes 4min)；Be put into after aluminium foil is washed the aluminium of 1-3Wt% nitric acid and 0.5-3Wt% from
In sub- solution, 4min is processed at a temperature of 70 DEG C；Treatment 5min in 95 DEG C of air dry oven is put into after washing.
Bending and specific volume method of testing to obtained etched foil is as follows：
Bending is tested：Test specimens size is 10mm*150mm (rush sample burr and should be less than 0.1mm), uses YAFENG companies
MIT-DA model bending testers, test condition knee 1.0 ± 0.1mm of radius of curvature R, 2.5 ± 0.5N of loading, angle of bend
90 ± 2 °, bend 6 times/S of shuttle speed, 70 ± 2mm of upper lower chuck spacing；
Specific volume is tested：It is melted into using boric acid system, is embodied in tank liquor for boric acid 100g/L, ammonium pentaborate 0.9g/
L, the Ω cm, PH 3.5 ± 0.5 of resistivity 1650 ± 50, test specimens size (rushes sample burr should be less than for 500mm*10mm
0.1mm), test solution is 70g/L, and the Ω cm of resistivity 7500 ± 300,70 ± 2 DEG C of temperature, PH 4.6 ± 0.5 tests electric current
2 ± 0.2mA/ pieces.
The performance test of the etched foil of table 1
| Experimental group | Bending/return | Thickness after corrosion/μm | |
| 1-1 | 55 | 2.48 | 110 |
| 1-2 | 54 | 2.52 | 111 |
| 1-3 | 58 | 2.53 | 109 |
| 1-4 | 52 | 2.49 | 112 |
Embodiment 2
The μ m thick annealing light paper tinsel of G9 models 120 is closed using Xinjiang is many, cubic texture >=94%, its basic element is configured to Al
>=99.98%, other element species and its content are Pb 0.8-1.2ppm, Zn 5-7ppm, Mg 1.5-2.5ppm, Cu 45-
54ppm、Fe 11-14ppm、Si 15-17ppm、Ga 6-8ppm；In 1mol/L sodium hydroxide solutions, at 40 DEG C of temperature, leaching
Bubble 60Sec；It is put into after washing in 5Wt% sulfuric acid solutions, 120Sec is processed under 60 DEG C of temperature conditionss；In a list after washing
Group triangular pulse, positive dutycycle 70%, Mean Forward Current about 0.5A/cm2, one is applied on the basis of positive time 100ms
Individual to continue 8A perseverance direct currents, its current diagram is shown in accompanying drawing 2, and corrosion 80Sec is powered up at a temperature of 72 DEG C；It is put into after washing
In 5Wt% dilute phosphoric acid solutions, 120Sec is processed at a temperature of 60 DEG C；Paillon foil is put into second-level groove, tank liquor composition proportion is
The calcium polystyreme sulphonate of the nitric acid of 8Wt%, 0.3% aluminium ion and 0.01Wt%, it is close in electric current using 4 electrolytic cells of V
Degree 0.1A/cm2, electrochemical corrosion 12min (i.e. each V processes 3min) under conditions of temperature 70 C；It is put into after aluminium foil is washed
In the aluminium ion solution of 1-3Wt% nitric acid and 0.5-3Wt%, 4min is processed at a temperature of 70 DEG C；95 DEG C are put into after washing
5min is processed in air dry oven.With embodiment 1, test result is shown in Table 2 to method of testing.
The performance test of the etched foil of table 2
| Experimental group | Bending/return | Thickness after corrosion/μm | |
| 2-1 | 58 | 0.634 | 112 |
| 2-2 | 56 | 0.662 | 111 |
| 2-3 | 54 | 0.641 | 112 |
| 2-4 | 52 | 0.642 | 113 |
Embodiment 3
From the firmly light thickness of 1N99 models 110 annealing light paper tinsel, cubic texture >=96%, its basic element be configured to Al >=
99.98%, other element species and its content are Cu 55ppm, Fe 8-11ppm, Si 10-13ppm；In 0.5mol/L hydrogen-oxygens
Change in sodium solution, at 38 DEG C of temperature, soak 100Sec；It is put into after washing in the nitration mixture of 5Wt% sulfuric acid and 4Wt% nitric acid composition,
60Sec is processed under 55 DEG C of temperature conditionss；One-level hair engaging aperture is carried out after washing, electric current is in a just profound wave impulse of single group, just
To dutycycle 60%, Mean Forward Current about 0.4A/cm2, applying one on the basis of positive time 200ms, to continue 15A permanent straight
Stream, its current diagram is shown in accompanying drawing 3, and corrosion 70Sec is powered up at a temperature of 70 DEG C；5Wt% dilute phosphoric acid solutions are put into after washing
In, process 120Sec at a temperature of 60 DEG C；Paillon foil is put into second-level groove, tank liquor composition proportion is nitric acid, 0.5% of 10Wt%
Aluminium ion and 0.05Wt% calcium polystyreme sulphonate, using 3 electrolytic cells of V, in current density 0.1A/cm2, temperature 65
Electrochemical corrosion 9min (i.e. each V processes 3min) under conditions of DEG C；1-3Wt% nitric acid and 0.5- are put into after aluminium foil is washed
In the aluminium ion solution of 3Wt%, 4min is processed at a temperature of 70 DEG C；Treatment in 95 DEG C of air dry oven is put into after washing
5min.Method of testing is with embodiment 1.
The performance test of the etched foil of table 3
| Experimental group | Bending/return | Thickness after corrosion/μm | |
| 3-1 | 48 | 0.852 | 111 |
| 3-2 | 52 | 0.862 | 110 |
| 3-3 | 56 | 0.841 | 113 |
| 3-4 | 52 | 0.856 | 112 |
As can be seen from the table, there is preferable mechanical performance and higher by the etched foil prepared by the method for the present invention
Specific volume.
Claims (7)
1. a kind of method that mesohigh etched foil is prepared with pulse direct current superimposed current, it is characterised in that comprise the following steps：
A) previous treatment：Light paper tinsel raw material is put into the sodium hydroxide solution of 0.5-1mol/L, 60- is processed at 30-40 DEG C
120Sec；
B) the first two treatment：It is that 1-5Wt% sulfuric acid and 10-20Wt% nitric acid are mixed that the above-mentioned aluminium foil by previous treatment is put into concentration
Close in solution, 90-120Sec is processed at 55-70 DEG C；
C) one-level hair engaging aperture：It is the sulfuric acid of 30-50Wt%, 3-5Wt% by concentration is put into by the aluminium foil after above-mentioned the first two treatment
In hydrochloric acid, the aluminum ions tank liquor of 1-2Wt%, 50-80Sec is electrolysed at 60-80 DEG C；
D) treatment in：To be put into 3-5Wt% dilute phosphoric acid solutions by the aluminium foil of hair engaging aperture step process, in 55-65 DEG C for the treatment of
120-180Sec；
E) two grades of hair engaging aperture：The aluminium foil that will be processed in process is put into nitric acid, the 0.2-0.5Wt% that tank liquor composition proportion is 5-8Wt%
Aluminium ion and 0.01-0.5Wt% calcium polystyreme sulphonate solution in, in 65-80 DEG C of direct current power-up treatment 12-18min；
F) post-process：To be put into the aluminum ions solution of nitric acid containing 1-3Wt%, 0.5-3Wt% by the aluminium foil of two grades of hair engaging aperture,
60-70 DEG C of immersion 3-4min；
G) dry：2-5min is processed in 80-120 DEG C of air dry oven by being put into by the aluminium foil of post processing, foil closing after drying；
Characterized in that, the one-level hair engaging aperture applies the superimposed current that Faradaic current is DC pulse.
2. the method that mesohigh etched foil is prepared with pulse direct current superimposed current according to claim 1, it is characterised in that
The smooth paper tinsel raw material be by high-temperature vacuum stepped annelaing process, thickness be 110-130 μm, cubic texture >=92% it is high-purity
Aluminium foil.
3. the method that mesohigh etched foil is prepared with pulse direct current superimposed current according to claim 1, it is characterised in that
Purity >=99.98% of the smooth paper tinsel raw material, the content of wherein impurity element Pb, Zn, Mg, Cu, Fe and Si is respectively 0-
1.0ppm、2-3ppm、3-7ppm、40-70ppm、5-15ppm、5-25ppm。
4. the method that mesohigh etched foil is prepared with pulse direct current superimposed current according to claim 1, it is characterised in that
Phosphide element and Ce elements are added with the treatment fluid of previous treatment, its content is respectively 60-90ppm and 20-40ppm.
5. the method that mesohigh etched foil is prepared with pulse direct current superimposed current according to claim 1, it is characterised in that
The superimposed current be 10-20A it is small it is galvanic on the basis of increase a single group or many group pulses, wherein positive dutycycle is
50-80%, Mean Forward Current is 0.4-0.8A/cm2, the positive time is 100ms.
6. the method that mesohigh etched foil is prepared with pulse direct current superimposed current according to claim 1, it is characterised in that
3-4 electrolytic cell is used during two grades of hair engaging aperture, the calcium polystyreme sulphonate of 0.01-0.03Wt%, electricity are added in tank liquor composition
Current density 0.05-0.1A/cm2。
7. the method that mesohigh etched foil is prepared with pulse direct current superimposed current according to claim 1, it is characterised in that
Using aluminum ions nitric acid weak solution is contained, concentration of nitric acid is 1-2Wt%, and aluminium ion concentration is 1-2Wt% for post processing.
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| CN104835647B (en) * | 2015-04-28 | 2017-09-01 | 乳源瑶族自治县东阳光化成箔有限公司 | A kind of anodic attack foil making method and a kind of aluminium foil corrosion electrolytic cell |
| CN106409514A (en) * | 2015-08-01 | 2017-02-15 | 东莞东阳光科研发有限公司 | Corrosion method for ultra-high-voltage and high-specific-capacity positive electrode corrosion foil |
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| CN105957717B (en) * | 2016-05-26 | 2018-11-30 | 乳源县立东电子科技有限公司 | The multiple hair engaging aperture method of the multistage of mesohigh anode foils |
| CN108364791B (en) * | 2018-03-23 | 2019-12-06 | 广西贺州市桂东电子科技有限责任公司 | Method for producing special hole type aluminum electrolysis anode corrosion foil |
| CN108396367B (en) * | 2018-05-31 | 2020-09-22 | 南通海星电子股份有限公司 | Method for manufacturing medium-high voltage corrosion foil for aluminum electrolytic capacitor |
| CN109609991B (en) * | 2018-12-26 | 2020-03-24 | 东莞东阳光科研发有限公司 | Formed foil, preparation method and application thereof |
| CN109554746B (en) * | 2018-12-26 | 2020-08-04 | 乳源瑶族自治县东阳光化成箔有限公司 | Method for manufacturing high-pressure high-specific-volume corrosion foil |
| CN109797424B (en) * | 2018-12-28 | 2021-08-10 | 广西贺州市桂东电子科技有限责任公司 | Method for treating five-level pore formation corrosion of medium-high voltage anode aluminum foil |
| CN112117128B (en) * | 2020-08-05 | 2022-04-22 | 乳源瑶族自治县东阳光化成箔有限公司 | High-specific-volume and high-strength medium-high voltage corrosion electrode foil and preparation method and application thereof |
| CN112080787B (en) * | 2020-08-14 | 2022-04-29 | 乳源瑶族自治县东阳光化成箔有限公司 | Corrosion foil for aluminum electrolytic capacitor and preparation method thereof |
| CN113470975B (en) * | 2021-06-17 | 2022-05-17 | 新疆众和股份有限公司 | Ultrahigh specific volume electrode foil and preparation method thereof |
| CN114141542B (en) * | 2021-11-29 | 2023-12-29 | 江苏立富电极箔有限公司 | Direct current and pulse superposition corrosion process |
| CN114032606A (en) * | 2021-12-22 | 2022-02-11 | 江苏立富电极箔有限公司 | Method for preparing medium-high pressure corrosion foil by using phosphoric acid as corrosion inhibitor in corrosion process |
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