CN102568858A - Production method of high dielectric constant composite alumina film - Google Patents
Production method of high dielectric constant composite alumina film Download PDFInfo
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- CN102568858A CN102568858A CN2012100109594A CN201210010959A CN102568858A CN 102568858 A CN102568858 A CN 102568858A CN 2012100109594 A CN2012100109594 A CN 2012100109594A CN 201210010959 A CN201210010959 A CN 201210010959A CN 102568858 A CN102568858 A CN 102568858A
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- aluminium foil
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- aluminum foil
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011888 foil Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000005030 aluminium foil Substances 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 34
- 239000003292 glue Substances 0.000 claims description 30
- 229910021645 metal ion Inorganic materials 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 27
- 239000002738 chelating agent Substances 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- -1 phosphatide Chemical compound 0.000 claims description 7
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001741 Ammonium adipate Substances 0.000 claims description 6
- 235000019293 ammonium adipate Nutrition 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 4
- 229940094800 barium oxalate Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- BZRSOWBAZCOWRN-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO BZRSOWBAZCOWRN-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KKSAZXGYGLKVSV-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO KKSAZXGYGLKVSV-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- YXADBYBKMNNRPQ-UHFFFAOYSA-N heptanoic acid;zirconium Chemical compound [Zr].CCCCCCC(O)=O YXADBYBKMNNRPQ-UHFFFAOYSA-N 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BPYXFMVJXTUYRV-UHFFFAOYSA-J octanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O BPYXFMVJXTUYRV-UHFFFAOYSA-J 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a production method of high dielectric constant composite alumina film, which can improve the specific capacity of an anode foil for an aluminum electrolysis capacitor. By improving the present industrial production line, high dielectric constant oxide is introduced on the surface of a corrosion aluminum foil, and a composite alumina film medium layer having high dielectric constant can be formed through the nanometer compounding. A layer of high dielectric constant oxide precursor is deposited on the surface of the surface modified corrosion aluminum foil through a wet chemical method, gradient heat treatment is performed on the corrosion aluminum foil after hydrolyzation, then the corrosion aluminum foil is soaked into the formation solution to be subjected to the nanometer compounding so as to obtain a layer of the nanometer composite alumina film having the high dielectric constant, so the specific capacity of the corrosion aluminum foil can be improved. Compared with the composited aluminum foil which is not treated, the aluminum foil which is treated by the method provided by the invention has the advantages that the specific capacity of the aluminum foil can be improved by 20 to 50 percent. The production method can be linked with the present industrial electrochemistry corrosion extended surface.
Description
Technical field
The invention belongs to technical field of electronic materials, be specifically related to the production method of aluminium electrolytic capacitor with high-k composite alumina film.
Background technology
Aluminium electrolytic capacitor is one of base electronic element very important in electric, the electronic system.Along with 3C (Computer; Communication; Consumer electronic) fast development of industry; Electronic product constantly strides forward towards miniaturization, lightweight direction, as discrete component-aluminium electrolytic capacitor indispensable in the circuit---equally also be badly in need of developing to miniaturization, lightweight direction.
Aluminium electrolytic capacitor is formed by the anode aluminium foil that forms the alumina medium film through excessive erosion and anodic oxidation, electrolyte and through the cathode aluminum foil of excessive erosion; Because the cathode aluminum foil capacitance is far above anode aluminium foil; Therefore, the capacitance of aluminium electrolytic capacitor is mainly determined by anode aluminium foil.By specific volume formula C=ε Sd
-1Can know that the material that the dielectric constant ratio aluminum oxide is high is compound in the alumina medium, can increase the medium DIELECTRIC CONSTANTS, improve the anode aluminium foil specific volume, reduce the anode aluminium foil consumption, realize the miniaturization and the lightweight of aluminium electrolytic capacitor.
At present more existing researchers apply high dielectric constant oxide to aluminium foil surface and launch research; The aluminium foil specific volume obtains certain raising; But all only for prepared in laboratory; Special study the basic not report of technology that supporting suitable industry links on a large scale and produces therewith, and traditional production technology utmost point does not match.
Summary of the invention
The purpose of this invention is to provide link the on a large scale interlock production method of the high-k composite alumina film produced of a kind of suitable industry; To improve the aluminium electrolytic capacitor specific volume, realize corroding the production method of the high-k composite alumina film that expanding looks unfamiliar produces with present electrochemistry in industry.
For achieving the above object, the technical scheme that the present invention adopts is:
1) presoma glue configuration: adopting wet chemical method is that 1: 1 mixed gets mixture with solubility organic metal salt and metal inorganic salt by metal ion mol ratio; Then mixture is joined and get mixed solution in the chelating agent; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 5～20; To regulate the concentration of mixed solution metal ion be 0.001～0.5mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.001～0.1mol/L that corrosive aluminum foil is immersed in concentration, and temperature is 20～80 ℃ silane, mercaptan, phosphatide, sulfonate, polyethylene glycol, polyvinyl alcohol, tween or takes charge of in the shift report face modifier solution, soaks 60～600S;
3) aluminium foil surface applies: it is in 20～80 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 10～300S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 10～300S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 0.3～3m/min, is that 20～150 ℃/m rises to 300～630 ℃ from room temperature with temperature gradient, at constant temperature heat treatment 60～600S of 300～630 ℃;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 3～10%, temperature is in 60～95 ℃ the ammonium adipate or boric acid, loads 6～600V voltage, 10～100A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 0.05～10%, temperature is in 20～90 ℃ phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphomolybdate or the teos solution; Soak 10～600S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
In the n-butanol salt that described solubility organic metal salt is Ti, Ta, Zr, Nb, isopropoxide, caprylate, the enanthate one or both.
Described metal inorganic salt is one or both in the acetate, oxalates, nitrate of Ca, Ba, Bi, Sr.
Described chelating agent is a kind of or two kinds in ethylenediamine tetra-acetic acid, acetylacetone,2,4-pentanedione, lactic acid, the urea.
The present invention adopts wet-chemical to be deposited as film method, at first to the corrosive aluminum foil surface modification, then at its superficial growth one deck high dielectric constant oxide presoma; After the hydrolysis, gradient heat treatment forms high dielectric nano-oxide film; Again that electrochemical nano in the aluminium foil immersion formation liquid is compound; Formation has the nano combined deielectric-coating of high-k, improves the specific volume of anode aluminium foil, at last aluminium foil is immersed in the methanol treatment fluid; Strengthen the water-fast and property of aluminium foil, to improve the useful life of aluminium electrolytic capacitor.Compare with untreated formed aluminum foil, the present invention can improve aluminium foil specific volume 20～50%, untreated 20Vf formed aluminum foil specific capacity 70-82 μ F/cm
2, aluminium foil specific capacity 84-123 μ F/cm of the present invention
2
Embodiment
Embodiment 1:
1) presoma glue configuration: adopting wet chemical method is that 1: 1 mixed gets mixture with n-butanol titanium and acetate calcium by metal ion mol ratio; Then mixture is joined and get mixed solution in the chelating agent ethylenediamine tetra-acetic acid; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 8; To regulate the concentration of mixed solution metal ion be 0.001mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.005mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 30 ℃ the silane surface modified agent solution, soaks 100S;
3) aluminium foil surface applies: it is in 30 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 50S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 100S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 0.3m/min, is that 150 ℃/m rises to 500 ℃ from room temperature with temperature gradient, at 500 ℃ of constant temperature heat treatment 100S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 5%, temperature is in 75 ℃ the ammonium adipate, loads 100V voltage, 10A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 3%, temperature is in 30 ℃ the phosphoric acid solution, soaks 100S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 2:
1) presoma glue configuration: adopting wet chemical method is that 1: 1 mixed gets mixture with isopropyl alcohol tantalum and barium oxalate by metal ion mol ratio; Then mixture is joined and get mixed solution in the chelating agent acetylacetone,2,4-pentanedione; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 10; To regulate the concentration of mixed solution metal ion be 0.003mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.03mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 50 ℃ the mercaptan surface modification agent solution, soaks 300S;
3) aluminium foil surface applies: it is in 50 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 200S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 80S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 1m/min, is that 120 ℃/m rises to 300 ℃ from room temperature with temperature gradient, at 300 ℃ of constant temperature heat treatment 300S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 7%, temperature is in 85 ℃ the boric acid, loads 300V voltage, 50A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 6%, temperature is in 50 ℃ the ammonium dihydrogen phosphate, soaks 300S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 3:
1) presoma glue configuration: adopting wet chemical method is that 1: 1 mixed gets mixture with zirconium caprylate and bismuth nitrate by metal ion mol ratio; Then mixture is joined and get mixed solution in the chelating agent lactic acid; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 5; To regulate the concentration of mixed solution metal ion be 0.005mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.001mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 20 ℃ the phosphatide surface modification agent solution, soaks 500S;
3) aluminium foil surface applies: it is in 20 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 100S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 50S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 0.5m/min, is that 135 ℃/m rises to 600 ℃ from room temperature with temperature gradient, at 600 ℃ of constant temperature heat treatment 500S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 3%, temperature is in 65 ℃ the ammonium adipate, loads 6V voltage, 30A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 0.5%, temperature is in 20 ℃ the ammonium phosphomolybdate solution, soaks 500S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 4:
1) presoma glue configuration: adopting wet chemical method is that 1: 1 mixed gets mixture with enanthic acid niobium and strontium acetate by metal ion mol ratio; Then mixture is joined and get mixed solution in the chelating agent urea; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 12; To regulate the concentration of mixed solution metal ion be 0.1mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.08mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 40 ℃ the sulfonate surface modification agent solution, soaks 200S;
3) aluminium foil surface applies: it is in 40 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 80S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 200S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 1.6m/min, is that 100 ℃/m rises to 400 ℃ from room temperature with temperature gradient, at 400 ℃ of constant temperature heat treatment 200S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 6%, temperature is in 90 ℃ the boric acid, loads 600V voltage, 80A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 8%, temperature is in 40 ℃ the teos solution, soaks 200S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 5:
1) presoma glue configuration: adopting wet chemical method is that 0.3: 0.7: 1 mixed gets mixture with n-butanol tantalum, isopropyl titanate and barium oxalate by metal ion mol ratio; Then with mixture join in the mixture of chelating agent ethylenediamine tetra-acetic acid and acetylacetone,2,4-pentanedione mixed solution; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 15; To regulate the concentration of mixed solution metal ion be 0.3mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.05mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 60 ℃ the polyethylene glycol surface modification agent solution, soaks 60S;
3) aluminium foil surface applies: it is in 60 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 300S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 150S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 3m/min, is that 20 ℃/m rises to 350 ℃ from room temperature with temperature gradient, at 350 ℃ of constant temperature heat treatment 60S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 8%, temperature is in 60 ℃ the ammonium adipate, loads 200V voltage, 40A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 0.05%, temperature is in 60 ℃ the phosphoric acid solution, soaks 10S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 6:
1) presoma glue configuration: adopting wet chemical method is that 1: 0.4: 0.6 mixed gets mixture with sad niobium and calcium acetate, barium oxalate by metal ion mol ratio; Then with mixture join in the mixture of chelating agent lactic acid and urea mixed solution; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 20; To regulate the concentration of mixed solution metal ion be 0.5mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.01mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 80 ℃ the polyvinyl alcohol surface modification agent solution, soaks 400S;
3) aluminium foil surface applies: it is in 80 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 10S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 260S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 2m/min, is that 50 ℃/m rises to 560 ℃ from room temperature with temperature gradient, at 560 ℃ of constant temperature heat treatment 400S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 10%, temperature is in 95 ℃ the ammonium adipate, loads 80V voltage, 35A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 1.5%, temperature is in 80 ℃ the ammonium dihydrogen phosphate, soaks 400S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 7:
1) presoma glue configuration: adopting wet chemical method is 0.8: 0.2: 0.1 with sad titanium, enanthic acid zirconium and bismuth acetate, strontium oxalate by metal ion mol ratio: 0.9 mixed gets mixture; Then with mixture join in the mixture of chelating agent ethylenediamine tetra-acetic acid and urea mixed solution; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 18; To regulate the concentration of mixed solution metal ion be 0.2mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.1mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in 70 ℃ the tween surface modification agent solution, soaks 600S;
3) aluminium foil surface applies: it is in 70 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 150S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 300S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 1.3m/min, is that 80 ℃/m rises to 630 ℃ from room temperature with temperature gradient, at 630 ℃ of constant temperature heat treatment 600S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 4%, temperature is in 70 ℃ the boric acid, loads 500V voltage, 100A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 10%, temperature is in 90 ℃ the ammonium phosphomolybdate solution, soaks 600S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Embodiment 8:
1) presoma glue configuration: adopting wet chemical method is 0.5: 0.5: 0.6 with n-butanol tantalum, isopropyl alcohol niobium and strontium acetate, barium oxalate by metal ion mol ratio: 0.4 mixed gets mixture; Then with mixture join in the mixture of chelating agent acetylacetone,2,4-pentanedione and lactic acid mixed solution; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 16; To regulate the concentration of mixed solution metal ion be 0.4mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.07mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in department's shift report face modifier solution of 50 ℃, soaks 350S;
3) aluminium foil surface applies: it is in 50 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 260S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 10S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 2.8m/min, is that 40 ℃/m rises to 460 ℃ from room temperature with temperature gradient, at 460 ℃ of constant temperature heat treatment 350S;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 9%, temperature is in 80 ℃ the boric acid, loads 400V voltage, 60A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 7%, temperature is in 90 ℃ the teos solution, soaks 80S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
Facilities and equipments of the present invention are simple, with short production cycle, adopt water solution system fully, and are environmentally friendly, can realize interlock with present electrochemistry in industry corrosion expansion face or anodic oxidation production line.
Claims (4)
1. the production method of high-k composite alumina film is characterized in that:
1) presoma glue configuration: adopting wet chemical method is that 1: 1 mixed gets mixture with solubility organic metal salt and metal inorganic salt by metal ion mol ratio; Then mixture is joined and get mixed solution in the chelating agent; Metal ion in the mixture wherein: the mol ratio of chelating agent=1: 5～20; To regulate the concentration of mixed solution metal ion be 0.001～0.5mol/L to water again, and regulating pH value simultaneously and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.001～0.1mol/L that corrosive aluminum foil is immersed in concentration, and temperature is 20～80 ℃ silane, mercaptan, phosphatide, sulfonate, polyethylene glycol, polyvinyl alcohol, tween or takes charge of in the shift report face modifier solution, soaks 60～600S;
3) aluminium foil surface applies: it is in 20～80 ℃ the presoma glue that the corrosive aluminum foil after the surface modification is immersed in temperature, soaks 10～300S;
4) presoma hydrolysis: the aluminium foil that surfaces coated is covered with presoma is immersed in the hydrolytic tank, hydrolysis 10～300S;
5) presoma heat treatment: aluminium foil is sent in the high temperature furnace with the feeding rate of 0.3～3m/min, is that 20～150 ℃/m rises to 300～630 ℃ from room temperature with temperature gradient, at constant temperature heat treatment 60～600S of 300～630 ℃;
6) nano combined: with the aluminium foil after the heat treatment be immersed in that mass concentration is 3～10%, temperature is in 60～95 ℃ the ammonium adipate or boric acid, loads 6～600V voltage, 10～100A/m
2Electric current carries out anodic oxidation, forms nano combined deielectric-coating;
7) water-fastly close processing: with the aluminium foil after the anodic oxidation be immersed in that mass concentration is 0.05～10%, temperature is in 20～90 ℃ phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphomolybdate or the teos solution; Soak 10～600S, repeating step 6 again) the nano combined high-k composite alumina film that obtains.
2. the production method of high-k composite alumina film according to claim 1 is characterized in that: one or both in the n-butanol salt that described solubility organic metal salt is Ti, Ta, Zr, Nb, isopropoxide, caprylate, the enanthate.
3. the production method of high-k composite alumina film according to claim 1 is characterized in that: described metal inorganic salt is one or both in the acetate, oxalates, nitrate of Ca, Ba, Bi, Sr.
4. the production method of high-k composite alumina film according to claim 1 is characterized in that: described chelating agent is a kind of or two kinds in ethylenediamine tetra-acetic acid, acetylacetone,2,4-pentanedione, lactic acid, the urea.
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