A kind of aluminum or aluminum alloy surface film oxide and preparation method thereof
Technical field
The present invention relates to a kind of preparation method and aluminum or aluminum alloy surface film oxide obtained by this method of aluminum or aluminum alloy surface film oxide.
Background technology
Aluminium alloy due to lightweight, specific tenacity is high, more and more wider in the application of the every field of national economy and national defense construction.Particularly the application on the carrier-borne product in modern national defense field has been only second to iron and steel, accounts for second.Yet aluminium alloy in actual applications, distinct issues are that " three is anti-" (preventing salt fog, damp and hot, mould) performance haves much room for improvement.Especially in harsh marine corrosion environment, due to the acting in conjunction of the corrosion factors such as the etch that is subject to high humidity and sea-salt fine particle, pitting, hard power cracking, the life-span of alloy product shortens greatly.Because applying to exist, aluminum alloy surface produces the underfilm corrosion problem because bonding force is bad; alloy product under the military service Yu Haiyang climatopes such as many Shipborne Electronic Equipment, radar and ocean weaponry; all with the surface electrochemistry conversion film as the rot-resistant first-selection; this zone of oxidation generated with electrolysis mode; can protect metal base; prevent its corrosion and weathering, increase surperficial flintiness and wear resisting property.
In numerous aluminium surface conversion coating technique, only have the corrosion resistance nature of differential arc oxidation can be called outstanding (the anti-neutral salt spray test time can reach 600h), but, due to reasons such as differential arc oxidation film forming overtension, difficulty of processing are large, the dimensional change amount is large, its application in electronics and each field of equipment is restricted.At present in the world, the Conversion Coatings on Aluminum Alloys that the surface anticorrosion of take separately is purpose, the effective employing anode oxidation process that is still.Aluminum anodized film is combined with matrix firmly, hard wear resistant, and thermotolerance is very outstanding, but the anti-neutral salt spray test time seldom surpasses 336h(14 cycle), this corrosion resisting property is substantially enough at general applied environment, but has become a difficult problem under ocean environment.Generally praise highly in the world by improving the oxidation filming quality and improve anti-corrosion capability, its process means is numerous, mainly contains: improve film density, reduce its porosity; Increase oxide thickness; Change oxide film self current potential.
Anodised film forming characteristics are: the atomic oxygen that anode produces is combined with body aluminium, generates the aluminium sesquioxide rete.The further growth of oxide film, be by the dual function of anode electric field and electrolytic solution dissolving, makes atomic oxygen arrive the aluminium body, forms oxide film.So aluminum anodized film is comprised of non-porous layer and porous layer (being called again blocking layer) two portions.The anode oxidation process generally adopted has: sulphuric acid anodizing, oxalic acid anodizing and nitration mixture hard anodizing.The aftertreatment hole-sealing technology matched with it has: F-Ni system low temperature pore sealing method, dichromate pore sealing method, boiling water high temperature hole sealing method etc.The barrier propterty that is to say anode oxide film is by the lifting common guarantee of quality of forming film and sealing quality, there is no such understanding, does not just have high-quality anti-seawater oxide film.
CN1272469 C, by the method for the sacrificial aluminium alloy anode of interpolation cerium (Ce), makes the obvious refinement of aluminium alloy crystal grain, and more even, has reduced the degree of oxidation of aluminium and the current potential of impurity phase, has reduced the corrosion that microbattery (claiming again galvanic couple) causes.
The people such as Lu Min adopt the electrochemistry approach, in aluminium alloy electrolysis process, nano levelly containing silicon particle, be prepared into and mix the silicon complex oxide film mixing in electrolytic solution, this oxide film has embodied the process of silicon and metal codeposition, film density has improved 10%, porosity reduces nearly four times, has obtained good barrier propterty.
These two kinds of methods were very obvious to the improvement of oxide film protective capacities in the last few years, but the former has just solved the micro-cell corrosion problem; And the latter is mainly by reducing the porosity of oxide film, improved rete density, to a certain degree promoted the barrier propterty of oxide film.They can't resist the salt fog under ocean environment, the corrosion failure that damp and hot, mould is caused simultaneously.
Promoting the protective of oxide film by improving sealing of hole, is another kind of striving direction.
A kind of method of sealing of hole processing of the anodizing of aluminium film being carried out with silicate solutions is arranged, but the aluminum oxide rete that this method makes is very thin, the standard that the sealing of hole time also need to reach far below conventional industry.Experiment shows, although aluminium and silicon have good avidity, the oxide film of making the sealing of hole processing of silicate has obviously promoted its alkaline resistance properties, and other aspects are not improved.
Summary of the invention
In order to overcome the above problems, the invention provides a kind of preparation method and oxide film obtained by this method of aluminum or aluminum alloy surface film oxide.By changing aluminium alloy anode oxide thin film-forming method and aftertreatment hole-sealing technology method, the filmogen of the different functionalities that anodic oxidation and sealing of hole are produced is superimposed upon on same oxide film, this oxide film has the good function that prevents salt fog, mould and damp and hot corrosion failure simultaneously, therefore be called " three is anti-" oxide film.
Technical program of the present invention lies in: to achieve these goals, the invention provides a kind of preparation method of aluminum or aluminum alloy surface film oxide, it is characterized in that the method comprises the following steps: at first, aluminum or aluminum alloy forms oxide film by anodic oxidation in electrolytic solution, and described electrolytic solution comprises sulfuric acid, nano silicon, acrylic resin and rare earth metal cerium salt or neodymium salt; Then, carry out pre-sealing of hole processing, will put into the trivalent chromium pore-sealing liquid that contains nickel ion through anodised aluminum or aluminum alloy and carry out sealing of hole, make the sealing of hole degree of oxide film reach at least 90%; Finally, carry out the processing of second step sealing of hole, carry out the sealing of hole processing in the alkaline aqueous solution of the nanometer particle that contains acrylic resin and silicon-dioxide, then washing, drying, finally form the anode oxide film of processing through two step sealing of holes.
Each concentration of component of anodic oxidation electrolyte of the present invention is: sulfuric acid 150-200g/l, and nano silicon 1-3.5g/l, acrylic resin 0.9-3g/l, rare earth metal cerium salt or neodymium salt, count 0.5-1g/l with cerium or neodymium; Technological specification is: direct current or the pulse power for power acquisition, current density is 1-2A/dm
2, under the voltage of 18-22V, electrolysis 30-50min, tank liquor temperature 10-22 ℃.Process by this step, can obtain thickness and reach the aluminum anodized film more than 20 microns, nano silicon can select acidic silicasol or neutral silicon sol, and it can promote film density more than 15%; Mixing of acrylic resin, can play the effect of mould fungus inhibition, and it makes oxide film increase hydrophobicity simultaneously; Rare earth metal salt can be selected vitriol or the carbonate of cerium or neodymium, and it makes the obvious refinement of aluminium alloy crystal grain, and more even, has reduced the current potential of impurity phase in the aluminium alloy, has reduced the corrosion that microbattery causes.
Two zone of oxidation structures that this anode electrolysis generates, a kind of is the very thin non-porous layer (also crying blocking layer) formed in the top of substrate, can play the effect that prevents attack, its thickness is relevant with the one-tenth membrane voltage, and this layer probably accounts for 2% of rete total thickness; Another kind is the unformed oxide skin of porous, is the main component of anode oxide film.Therefore, sealing of hole becomes another means that oxide film strengthens protective capacities, for non-corrosibility reaches the strongest, must carry out the sealing of hole processing by the antianode oxide film.
The present invention takes dual sealing of hole to do the method for aftertreatment, has improved oxide film density and complex protection capability.
Pre-sealing of hole of the present invention is processed the pore-sealing liquid adopted and is comprised: chromium nitrate 1-2g/l, and fluorine zirconic acid 0.4-0.8g/l, trisodium citrate 0.4-0.6g/l, single nickel salt 0.01-0.03g/l, technological specification is: 35 ± 5 ℃ of temperature; PH value 4.5 ± 0.5, time 40 ± 1min or press 1min/ μ m and calculate.This trivalent chromium pore-sealing liquid that contains nickel ion, can make the sealing of hole degree of oxide film reach at least 90%.
Second step sealing of hole of the present invention is processed the pore-sealing liquid adopted and is comprised: acrylic resin 45-52g/l, acid esters 0.5-1g/l in dodecyl second, nano silicon 11-15g/l, glycol glycerin ether 5-10g/l, working specification is: under room temperature condition, soak 1-2min.By this, process, the oxide film surface produces the organic coating film that one deck has hydrophobic function.
The present invention also provides a kind of aluminum or aluminum alloy surface film oxide, and wherein, this oxide film is prepared by method of the present invention.
With existing technology relatively, the present invention has following outstanding advantages: anode oxide film has good resisting sea water erosion performance; Anode oxide film, when having good resisting sea water erosion performance, also possesses identical with other oxide film ornamental; Anode oxide film has good alkaline resistance properties.
Embodiment
Embodiment 1.
Commercial-purity aluminium " three is anti-" oxide film becomes film test.
Adopt commercial-purity aluminium 1050A, its consist of (massfraction, %): Si≤0.25,0.000≤Fe≤0.400, Cu≤0.05, Mn≤0.05, Mg≤0.05, Zn≤0.07, Ti≤0.05, other≤0.03, Al >=99.50.
By the test piece polishing, with carrying out again the alkali electroless oil removing after the acetone degreasing degreasing, then carry out anodic oxidation treatment.The anodic oxidation electrolyte formula: sulfuric acid 180g/l, acidic silicasol 1.5g/l, acrylic resin 0.9g/l, cerium salt 0.5g/l(is in cerium).In current density, be 2A/dm
2, electrolysis 30min under the condition that temperature is 20 ℃, then wash with deionized water, cold wind dries up.
The pre-pore-sealing liquid of preparation trivalent chromium: chromium nitrate 1.5g/l, fluorine zirconic acid 0.8g/l, trisodium citrate 0.6g/l, single nickel salt 0.03g/l, 35 ℃ of temperature; PH value 4.5 ± 0.5; Sample is put into to the sealing of hole groove, carry out the sealing of hole processing, after 10 minutes, sample is taken out, wash with deionized water, cold wind dries up.
Preparation organic sealing liquid: add acrylic resin 52g/l in the sealing of hole groove, acid esters 1g/l in dodecyl second, nano silicon 15g/l, glycol glycerin ether 7.5g/l.Sample is soaked to 3min at ambient temperature, wash with deionized water after taking-up, cold wind dries up.
Embodiment 2.
Duralumin " three is anti-" oxide film becomes film test.
Adopt duralumin 2A12, its consist of (massfraction, %): Si≤0.50,3.8≤Cu≤4.9,1.2≤Mg≤1.8, Zn≤0.30,0.30≤Mn≤0.90, Ti≤0.15, Ni≤0.10,0.000≤Fe≤0.500,0.000≤Fe+Ni≤0.5000, other≤0.15, surplus is aluminium content.
By the test piece polishing, with carrying out again the alkali electroless oil removing after the acetone degreasing degreasing, then carry out anodic oxidation treatment.Anodic oxidation electrolyte formula: sulfuric acid 200g/l, acidic silicasol 1.5g/l; Acrylic resin 0.9g/l; Cerium salt 0.5g/l(is in cerium), in current density, be 2A/dm
2, electrolysis 50min under the condition that temperature is 20 ℃, then wash with deionized water, cold wind dries up.
The pre-pore-sealing liquid of trivalent chromium in preparation embodiment 1, be poured in the sealing of hole groove, bathes 35 ℃ of temperature, sample put into to the sealing of hole groove and carry out sealing of hole processing taking-up after 20 minutes, with deionized water, washes, and cold wind dries up.
Organic sealing solution in preparation embodiment 1, be poured in the sealing of hole groove, at room temperature sample put into to the sealing of hole groove and carried out after sealing of hole is processed 3min taking out, and with deionized water, washes, and cold wind dries up, and completes sealing of hole and processes.
Embodiment 3.
Aluminium diecast alloy " three is anti-" oxide film becomes film test.
Adopt aluminium diecast alloy YL101, its consist of (massfraction, %): 9.0≤Si≤10.0, Cu≤0.6, Mn≤0.35,0.45≤Mg≤0.65, Fe≤1.0, Ni≤0.50, Zn≤0.40, Pb≤0.10, Sn≤0.15, all the other are aluminium content.
By the test piece polishing, with carrying out again the alkali electroless oil removing after the acetone degreasing degreasing, then carry out anodic oxidation treatment.Anodic oxidation electrolyte formula: sulfuric acid 200g/l, neutral silicon sol 2g/l; Acrylic resin 0.9g/l; Cerium salt 0.5g/l(is in cerium), in current density, be 1.5A/dm
2, temperature is electrolysis 30min under the condition under 20 ℃, then washes with deionized water, cold wind dries up.
The pre-pore-sealing liquid of preparation embodiment 1 trivalent chromium, be poured in the sealing of hole groove, bathes 35 ℃ of temperature, sample put into to the sealing of hole groove and carry out sealing of hole processing taking-up after 20 minutes, with deionized water, washes, and cold wind dries up.
Preparation embodiment 1 organic sealing solution, be poured in the sealing of hole groove, at room temperature sample put into to the sealing of hole groove and carried out after sealing of hole is processed 3min taking out, and with deionized water, washes, and cold wind dries up, and completes sealing of hole and processes.
Above-mentioned three kinds of samples have represented fine aluminium, wrought aluminium alloy, aluminium diecast alloy, result to " three anti-" performance tests of three kinds of Process on Aluminum Alloy Oxidation Film confirms, aluminium alloy prepared through multi-step by this class " three is anti-" oxide film, the more conventional aluminum anodized film of its barrier propterty generally exceeds more than 50%.
The concrete weather resistance performance of the oxide film of embodiment 1-3 in the following areas.
Clad aluminum or the test of Process on Aluminum Alloy Oxidation Film barrier propterty.
1. after 480h artificial atmosphere corrosion test salt-fog test (GB/T 10125-2012), surface does not change.
2. after 24h copper accelerated acetic acid salt spray test (GB/T 12967.3-2008), surface does not change.
3. after 240h cyclic damp heat test (GJB150.9-86), surface does not change.
4. after 28d mould test (GJB150.10-86), mildew is 0 grade.
5. after 100 ℃ of high temperature test of 1h (GJB150.3-86), there is no obvious crack on oxide film.