AU2020327479B2 - Electrolytic oxidation solution for use in aluminum alloy oxidative film formation, and method for aluminum alloy oxidative film formation - Google Patents
Electrolytic oxidation solution for use in aluminum alloy oxidative film formation, and method for aluminum alloy oxidative film formation Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 62
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 58
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 20
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims description 39
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 21
- 239000000243 solution Substances 0.000 description 55
- -1 aluminum ions Chemical class 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000008151 electrolyte solution Substances 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910002703 Al K Inorganic materials 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 239000010407 anodic oxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 1
- 239000007789 gas Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- BZWNJUCOSVQYLV-UHFFFAOYSA-H trifluoroalumane Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Al+3].[Al+3] BZWNJUCOSVQYLV-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
Abstract
Disclosed are an electrolytic oxidation solution for use in aluminum alloy oxidative film formation, and a method for aluminum alloy oxidative film formation. The electrolytic oxidation solution comprises the following components: 0.1-1 g/L of ammonium hydrogen difluoride, and 5-60 g/L of oxalic acid, the oxidation solution comprising Al
Description
[0001] The present disclosure relates to the technical field of surface treatment of aluminum alloy profiles, and specifically relates to a treatment technique for oxidative film formation using electrochemistry.
[0002] The surface oxidation treatment of aluminum alloy is mainly to generate a protective film on the surface of aluminum profiles. This film has protective, decorative and other functional characteristics to meet the needs of architectural aluminum anodizing, decorative aluminum anodizing, corrosion-protective aluminum anodizing and engineering aluminum anodizing. According to different use purposes and different performance requirements, the characteristics of films are fully utilized to meet different uses.
[0003] In the existing technology, electrolytic solutions are roughly divided into: barrier-type anodic oxide film electrolytic solutions such as boric acid, neutral borate, neutral phosphate, neutral tartrate, neutral citrate and neutral oxalate; and porous-type anodic oxide film electrolytic solutions such as sulfuric acid, oxalic acid, chromic acid, phosphoric acid, sulfuric acid and organic acid.
[0004] Porous-type oxidizing electrolytic solutions in existing technology have the problem that aluminum ions in the solution continuously increase over the electrolysis time, so in order to control the concentration of aluminum ions in the electrolytic solution, the electrolytic solution needs continuously discharging and replenishing with an electrolytic solution free of aluminum ions to maintain aluminum ions at its concentration range.
[0005] The oxidative film formation process in the existing technology is as follows:
[0006] Film formation process: 2A + 3H20 --* A1203+ 6H++ 6e
[0007] Film dissolution process: A1203 + 6H -- 2A1 3++ 3H20
[0008] Water breaks down at the cathode and produces gas as follows:
[0009] 6H20+ 6e- -- 3H2 T+ 60H
[0010] Taking sulfuric acid as an example, SO42- anions participate in the anodic reaction of aluminum, and finally produce an anodic oxide film containing sulfate ions:
[0011] 2A+6H+ - 2A1 3++3H27
[0012] 2A1 3++ 3H20+3SO 42 -- >[A1203]+3H2SO4
[0013] A 13++ XH20 + YSO42-- [Al(OH)Y(SO4)x]+ XH+
[0014] This is a process involving continuous film formation and film dissolution.
[0015] In the above oxidation, if the concentration of F and Cl- exceeds 50 g/g in the solution, the profile will appear corrosion spots, so it needs strictly controlling.
[0016] Regardless of the type of the porous oxide film production process to be used, the concentration of aluminum ions in the electrolytic solution continues to rise, which generally results in a beneficial effect when it is less than 10 g/L, but an adverse effect when it is more than g/L. In order to control the concentration of aluminum ions, part of the old tank solution is generally discharged to reduce the aluminum content, but the discharge of the electrolytic solution takes away a large amount of H2SO4, and the discharged A13+ ions cause environmental pollution since most of them are neutralized with lime and thus generate a large amount of solid waste, which cause a huge environmental protection burden. Therefore, the existing technology, which is the key process point generating a large amount of solid waste in the current aluminum profile enterprises, is not only environmentally unfriendly but also incurs additional production costs.
[0017] Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
[0018] In view of the shortcomings of the existing technology, it would be desirable to provide an electrolytic oxidation solution for use in aluminum alloy oxidative film formation. This electrolytic oxidation solution produces ionization equilibrium when aluminum ion concentration reaches about 0.lg/L, can be recycled without the need of replacement, and generates an oxide film which is an honeycomb-like and uniform organic-inorganic fluorine-containing oxide film with corrosion resistance, impact resistance, high hardness and high wear resistance.
[0019] In view of the shortcomings of the existing technology, it would also be desirable to provide a method of aluminum alloy oxidative film formation. This process method is simple and can solve the environmental protection problem as the electrolytic waste solution does not need replacing.
[0020] In accordance with a first aspect of the present invention there is provided an electrolytic oxidation solution for use in aluminum alloy oxidative film formation, comprising the following components:
ammonium hydrogen difluoride with a concentration of greater than or equal to 0.1 g/L and less than 1 g/L, and oxalic acid with a concentration of 5-60 g/L,
wherein the oxidation solution comprises A13+ at an equilibrium concentration of 0.01-1 g/L.
[0021] There is also described an electrolytic oxidation solution for use in aluminum alloy oxidative film formation comprising the following components: 0.1-1 g/L of ammonium hydrogen difluoride and 5-60 g/L of oxalic acid, wherein the oxidation solution comprises Al 3 at an equilibrium concentration of 0.01-1 g/L.
[0022] As a preferred technical solution, the electrolytic oxidation solution comprises the following components: 0.1-0.6 g/L of ammonium hydrogen difluoride and 10-40 g/L of oxalic acid, and he oxidation solution comprises Al 3 at an equilibrium concentration of 0.01-1 g/L.
[0023] In the present disclosure, the presence of F ions in the electrolytic oxidation solution reduces the chemical energy of Al, enabling an easier generation of Al 3 , and providing oxalic acid at the concentration of about 50 times of ammonium hydrogen difluoride ensures that Al3 can generate aluminum oxalate and participates in film formation. F ions also act as a catalyst in the reaction process, as the strong complexation of F ions to Al 3 accelerates the dissolution of the oxide film and the continuous formation of the porous oxide film layer. Oxalic acid participates in the combined action of anodized film formation-anodizing-chemical dissolution-chemical film formation. However, ifNH3HF concentration reaches about 1.5 g/L, it will produce film-dissolving effect instead. When the film thickness reaches about 10 m, the film will achieve an equilibrium between film formation and film dissolution and not increase anymore. When it is increased to about 5.0 g/L, the film dissolution is faster than the film formation during oxidation, resulting in a failure of oxide film formation and thus causing the continuous increase of the Al 3 concentration in the solution. The dissolution of the aluminum matrix mainly depends on the concentration of fluoride ions, while the film formation depends on oxalic acid, so coordinating the ratio of the two allows the film to achieve the equilibrium of dissolution and formation, enabling that the Al 3 concentration in the pretreatment system roughly maintains constant.
[0024] As an improved technical solution, the electrolytic oxidation solution further contains a component selected from the group consisting of a soluble fluoride salt, oxalate salt, sulfate salt and mixtures thereof. The fluoride salt, oxalate salt and sulfate salt are added in an amount of 0.1 g/L.
[0025] As a preferred technical solution, the electrolytic oxidation solution further contains a component selected from the group consisting of sodium fluoride, sodium oxalate, sodium sulfate and mixtures thereof. The addition of sodium fluoride or sodium oxalate can effectively increase the content of organic components in the oxide film, and aluminum hexafluoride, aluminum trifluoride and sulfate ions also participate in film formation. In addition, the addition of salts can also reduce resistance and reduce electrolysis energy consumption.
[0026] In another aspect of the present invention, there is provided a method of aluminum alloy oxidative film formation comprising performing electrolysis by use of the above-mentioned electrolytic oxidation solution to form a layer of organic-inorganic fluorine-containing oxide film on the surface of aluminum alloy under a combined action of chemical film formation and electrochemical film formation.
[0027] As an improved technical solution, the electrolysis is performed at a constant voltage of -60 v in a constant potential electrolysis manner.
[0028] As another improved technical solution, the electrolysis is performed at a constant current of 1-5 A/dm2 in a constant current electrolysis manner.
[0029] As a preferred technical solution, the electrolysis is performed for1 min - 6 h.
[0030] As a preferred technical solution, the thickness of the organic-inorganic fluorine- containing oxide film is 0.5-60 [m.
[0031] Adopting the above-mentioned technical solution render the present disclosure the beneficial effects of:
[0032] The electrolytic oxidation solution for use in aluminum alloy oxidative film formation of the present disclosure contains the following components: 0.1-1 g/L of ammonium hydrogen difluoride and 5-60 g/L of oxalic acid, with Al 3 being present in the oxidation solution at equilibrium concentration of 0.01-1 g/L. When the electrolytic oxidation solution of the present disclosure is used in electrolytic oxidative film formation, chemical film formation and electrochemical film formation will work together, resulting in fast film formation; and the aluminum ion in the oxidation solution generally achieves ionization equilibrium when its concentration reaches about 0.1 g/L, after that its concentration will not increase anymore, so that the oxidation solution can be recycled without the need of replacement. Therefore, compared with the existing technology, this disclosure can reduce solid waste discharge of A13' by about 50 tons, waste water discharge by 80% or more, and waste water oxygen consumption by 90% for the production of every 5,000 tons of profiles. Moreover, the oxide film produced from electrolysis of the present disclosure is an organic-inorganic fluorine-containing oxide film which is uniformly honeycomb-shaped and has a film porosity of 60% or more as a result of SEM+EDS detection and analysis. The formed oxide film contains approximately fluorine in an amount of 1-15%, C in an amount of 3-20% and 0 in an amount of 46%, and has the advantages of high corrosion resistance, high impact resistance, toughness, high wear resistance and a high hardness about 400 HV.
[0033] The method of oxidative film formation using the electrolytic oxidation solution of the present disclosure is simple and easy to control and has a fast film formation speed. The electrolysis can be carried out by using either constant potential electrolysis or constant current electrolysis, and can quickly result in a uniform honeycomb-like oxide film having a thickness of 5-20 m under an electrolysis time of 1-20 min. Moreover, the long-term test shows that Al ions of this electrolytic solution reach electrolytic equilibrium once its concentration reaches about 0.1 g/L in the electrolytic solution, and the aluminum ion concentration does not increase over more than 12 months. Furthermore, use of low electrolyte concentration and fluoride ions as an dissolving agent of electro-oxidation film (pore-dissolving agent) prevents the anodized film surface from local interference of other ions (such as pitting corrosion), and the chemical film formation and electrochemical film formation undergo qualitative changes together, reducing the effect of concentration on film formation. In addition, high current can also be used to accelerate film formation so as to reduce the oxidation cost.
[0034] The electrolysis method of the present disclosure can result in a colorless and transparent to golden yellow composite film by controlling the voltage, current density or the film-forming speed, or changing the film-forming composition.
[0035] The present disclosure will be further described below in conjunction with the accompanying drawings and examples.
[0036] FIG. 1 is the surface morphology of the oxide film with a thickness of 15 m of the present disclosure detected by SEM;
[0037] FIG. 2 is the surface morphology of the oxide film with a thickness of 20 m of the present disclosure detected by SEM;
[0038] FIG. 3 is the energy dispersive spectrum (EDS) analysis of a point in FIG. 1;
[0039] FIG. 4 is the energy dispersive spectrum (EDS) analysis of another point in FIG. 1;
[0040] FIG. 5 is the energy dispersive spectrum (EDS) analysis of a point in FIG. 2;
[0041] FIG. 6 is the energy dispersive spectrum (EDS) analysis of another point in FIG. 2; and
[0042] FIG. 7 is the XPS spectrum of a point in FIG. 1.
[0043] The present disclosure will be further illuminated below with reference to the accompanying drawings and examples. It should be understood that these examples are used to illustrate the present disclosure rather than to limit the scope of the present invention. In addition, it should be understood that after reading the contents taught by the present disclosure, those skilled in the art can make various changes or modifications to the present disclosure, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
[0044] As shown in FIGs. 1-2, all the oxide films generated by electrolysis with a film pore diameter below 100 nm of the present disclosure were uniformly honeycomb-shaped. Two arbitrarily selected points in FIG. 1 and FIG. 2 with thicknesses of 15 pm and 20 pm respectively were analyzed by EDS. Their energy dispersive spectra respectively correspond to FIG. 3 and FIG. 4, and FIG. 5 and FIG. 6 and the analysis results are shown in the following Table 1, Table 2, Table 3 and Table 4. As can be seen from the figures, C on the surface of the oxide film of the present disclosure mainly was present in the form of functional groups such as C-C, C-O or C=0, and F was present in the form of AlF3/Na3AlF6. This demonstrated that oxide film of the present disclosure involved chemical film forming process.
Table 1
Element Intensity Weight% Atomic% Corm.
CK 0.3255 3.86 6.21 OK 1.3311 46.31 56.00 FK 0.2894 6.82 6.95 Al K 0.9979 43.01 30.84 Totals 100.00 100.00
Table 2
Element Intensity Weight% Atomic% Cormn.
CK 0.3052 4.28 7.02 OK 1.2575 42.24 52.03 FK 0.3064 6.19 6.42 Al K 1.0222 47.29 34.54 Totals 100.00 100.00
Table 3
Element Intensity Weight% Atomic% Cormn.
CK 0.5012 3.89 6.33 oK 1.7520 46.80 57.22 FK 0.4827 2.33 2.40 Al K 1.1315 46.97 34.05 Totals 100.00 100.00
Table 4
Element Intensity Weight% Atomic% Corm. CK 0.5396 7.44 11.73
OK 1.7180 46.35 54.84 FK 0.4745 3.47 3.46 Al K 1.1169 42.73 29.97
Totals 100.00 100.00
[0045] According to GB/T 9790-1988 and GB/T12967.3-2008, the oxide film by conventional sulfuric acid method in the existing technology and the aluminum alloy oxide film of the present disclosure were tested for corrosion resistance and microhardness, and the results are as follows in Table 5.
Film thickness /ptm CASS/Time Corrosion resistance grade Microhardness /HV 10 16 Conventional sulfuric 24 >9 grade 150-180 acid method 15 20 48 Electrolytic oxidation 8 16 of the present 10 24 >9 grade 400-600 disclosure 12 48
[0046] It can be seen that the oxidefilms prepared according to the present disclosure were thinner, but had higher hardness and stronger corrosion resistance.
Example 1
[0047] An electrolytic oxidation solution for use in aluminum alloy oxidative film formation, containing 0.2 g/L of ammonium hydrogen difluoride and 10 g/L of oxalic acid with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.1 g/L, was prepared.
Example 2
[0048] An electrolytic oxidation solution for use in aluminum alloy oxidative film formation, containing 0.4 g/L of ammonium hydrogen difluoride and 20 g/L of oxalic acid with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.2 g/L, was prepared.
Example 3
[0049] An electrolytic oxidation solution for use in aluminum alloy oxidative film formation, containing 0.6 g/L of ammonium hydrogen difluoride and 30 g/L of oxalic acid with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.22 g/L, was prepared.
Example 4
[0050] An electrolytic oxidation solution containing 0.5 g/L of ammonium hydrogen difluoride, g/L of oxalic acid and 2 g/L of sodium fluoride with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.2 g/L, was used to perform electrolysis. The electrolysis was carried out at room temperature at a direct current density of 2.5 A/dm2 (constant current method) for 10 min.
Example 5
[0051] An electrolytic oxidation solution containing 0.6 g/L of ammonium hydrogen difluoride and 40 g/L of oxalic acid with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.18 g/L, was used to perform electrolysis. The electrolysis was carried out at room temperature at a direct current density of 3.0 A/dm2 (constant current method) for 15 min.
Example 6
[0052] An electrolytic oxidation solution containing 0.45 g/L of ammonium hydrogen difluoride, g/L of oxalic acid and 5 g/L of sodium oxalate with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.2 g/L, was used to perform electrolysis. The electrolysis was carried out at room temperature at a direct voltage of 40 v (constant voltage method) for 15 min.
Example 7
[0053] An electrolytic oxidation solution containing 0.55 g/L of ammonium hydrogen difluoride and 35 g/L of oxalic acid with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.2 g/L, was used to perform electrolysis. The electrolysis was carried out at room temperature at a direct voltage of 30 v (constant voltage method) for 20 min.
Example 8
[0054] An electrolytic oxidation solution containing 0.35 g/L of ammonium hydrogen difluoride and 38 g/L of oxalic acid with Al 3 being present in the oxidation solution at an equilibrium concentration of 0.21 g/L, was used to perform electrolysis. The electrolysis was carried out at room temperature at a direct voltage of 60 v (constant voltage method) for 30 min.
Comparative Example 1
[0055] The electrolytic oxidation solutions with a sulfuric acid concentration of 18 g/L were used to preform electrolysis by use of the existing sulfuric acid method. The electrolysis was carried out at a temperature of 18°C+1 at a current density of 1.5 A/dm2 for 30 min.
[0056] The thickness and hardness of the oxide films prepared in examples 4-8 and Comparative Example 1, as well as the film surface morphology and composition detected and analyzed by SEM+EDS are shown in Table 5.
Table 5
Items Thickness Film hardness Surface morphology Composition analysis Gant) (HV) Example 4 10 410 Bright, transparent and uniform honeycomb- Organic-inorganic film like film with a porosity of 67% containing fluorine Example 5 12 430 Bright, transparent and uniform honeycomb- Organic-inorganic film like film with a porosity of 68% containing fluorine Example 6 18 435 Bright, transparent and uniform honeycomb- Organic-inorganic film like film with a porosity of 70% containing fluorine Example 7 20 445 Bright, transparentand uniform honeycomb- Organic-inorganic film like film with a porosity of 72% containing fluorine Example 8 25 450 Bright, golden yellow and uniform Organic-inorganic film honeycomb-like film with a porosity of 65% containing fluorine Comparative 10 140 Film without honeycomb structure, having a Inorganic film free of Example 1 porosity of 18% fluorine
[0057] As can be seen from Table 5, the oxide films prepared by the present disclosure were uniformly honeycomb-shaped with a film porosity exceeding 65%, and were organic-inorganic combined fluorine-containing oxide film with high hardness. Besides, with the increase of electrolysis time within a certain range, their film thickness increased. In contrast, the inorganic film obtained in the comparative example was not honeycomb-shaped and free of fluorine, and had a film porosity of only 18% and low hardness.
Industrial Applicability
[0058] 1. The electrolytic oxidation solution for use in aluminum alloy oxidative film formation of the present disclosure contains the following components: 0.1-1 g/L of ammonium hydrogen difluoride and 5-60 g/L of oxalic acid, with Al 3 being present in the oxidation solution at equilibrium concentration of 0.01-1 g/L. When the electrolytic oxidation solution of the present disclosure is used in electrolytic oxidative film formation, chemical film formation and electrochemical film formation will work together, resulting in fast film formation; and the aluminum ion in the oxidation solution generally achieves ionization equilibrium when its concentration reaches about 0.1 g/L, after that its concentration will not increase anymore, so that the oxidation solution can be recycled without the need of replacement. Therefore, compared with the existing technology, this disclosure can reduce solid waste discharge of A13' by about 50 tons, waste water discharge by 80% or more, and waste water oxygen consumption by 90% for the production of every 5,000 tons of profiles. Therefore, it has promising industrial practicability.
[0059] 2. The oxide film produced from electrolysis of the present disclosure is an organic inorganic fluorine-containing oxide film which is uniformly honeycomb-shaped and has a film porosity of 60% or more as a result of SEM+EDS detection and analysis. The formed oxide film contains approximately fluorine in an amount of 1-15%, C in an amount of 3-20% and 0 in an amount of 46%, and has the advantages of high corrosion resistance, high impact resistance, toughness, high wear resistance and a high hardness about 400 HV. Therefore, it has promising industrial practicability.
[0060] 3. The method of oxidative film formation using the electrolytic oxidation solution of the present disclosure is simple and easy to control and has a fast film formation speed. The electrolysis can be carried out by using either constant potential electrolysis or constant current electrolysis, and can quickly result in a uniform honeycomb-like oxide film having a thickness of 5-20 m under an electrolysis time of 1-20 min. It can result in a colorless and transparent to golden yellow composite film by controlling the voltage, current density or the film-forming speed, or changing the film-forming composition. The process method is simple and controllable, so it has promising industrial practicability.
[0061] 4. Through long-term test, this electrolytic solution Al ions in the electrolytic solution produces electrolytic equilibrium at about 0.1 g/L, and aluminum ion concentration will not increase for more than 12 months. In addition, low electrolyte concentration and fluoride ions as electro-oxidation film solvent (porosity-dissolving agent) interfere with the phenomenon that other ions have local interference on the surface of the anodized film (such as pitting corrosion), and the chemical film formation and electrochemical film formation undergo qualitative changes together, reducing the effect of concentration on film formation. In addition, high current can also be used for quick film formation to reduce the cost of oxidation. Therefore, it has promising industrial practicability.
Claims (9)
1. An electrolytic oxidation solution for use in aluminum alloy oxidative film formation, comprising the following components: ammonium hydrogen difluoride with a concentration of greater than or equal to 0.1 g/L and less than 1 g/L, and oxalic acid with a concentration of 5-60 g/L, wherein the oxidation solution comprises Al 3 at an equilibrium concentration of 0.01-1 g/L.
2. The electrolytic oxidation solution for use in aluminum alloy oxidative film formation according to claim 1, comprising the following components: 0.1-0.6 g/L of ammonium hydrogen difluoride and 10-40 g/L of oxalic acid, wherein the oxidation solution comprises A13+ at an equilibrium concentration of 0.1-1 g/L.
3. The electrolytic oxidation solution for use in aluminum alloy oxidative film formation according to claim 1, further comprising a component selected from the group consisting of a soluble fluoride salt, oxalate salt, sulfate salt and mixtures thereof.
4. The electrolytic oxidation solution for use in aluminum alloy oxidative film formation according to claim 3, further comprising a component selected from the group consisting of sodium fluoride, sodium oxalate, sodium sulfate and mixtures thereof.
5. A method of aluminum alloy oxidative film formation, comprising performing electrolysis by use of the electrolytic oxidation solution according to any one of claims 1 to 4 to form a layer of organic-inorganic fluorine-containing oxide film on the surface of aluminum alloy under a combined action of chemical film formation and electrochemical film formation.
6. The method of aluminum alloy oxidative film formation according to claim 5, wherein the electrolysis is performed at a constant voltage of20-60 v in a constant potential electrolysis manner.
7. The method of aluminum alloy oxidative film formation according to claim 5, wherein the electrolysis is performed at a constant current of 1-5 A/dm2 in a constant current electrolysis manner.
8. The method of aluminum alloy oxidative film formation according to claim 5, wherein the electrolysis is performed for 1 min-6 h.
9. The method of aluminum alloy oxidative film formation according to claim 5, wherein the thickness of the organic-inorganic fluorine-containing oxide film is 0.5-60 [m.
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