A kind of processing method of aluminum alloy surface anodic oxidation-sealing of hole
Technical field
The present invention relates to the processing method of a kind of aluminum alloy surface anodic oxidation-sealing of hole, belong to metal surface treatment technology
Field.
Background technology
Anodic oxidation is a kind of electrolytic oxidation, and the surface of aluminium alloy is generally converted to layer oxide film in this process, this
It is functional that tunic has protectiveness, dicoration and other some.Oxide-film divides two big classes: Barrier oxide-film and porous type
Oxide-film, Barrier oxide-film is one layer of thin oxide film against the dense non-porous of metal surface, and thickness depends on applied voltage
It is usually no more than 0.1um.Porosity anodic oxide film is made up of barrier layer and porous layer two-layer oxide-film, barrier layer thickness and powering up outward
It is pressed with pass, the electricity that porous layer thickness is determined by.We are most commonly used that Porosity anodic oxide film.The feature of oxide-film has:
A. oxide-film structure is the cellular knot of porous, and the porous of film makes have good absorbability, can make the end of coated layer
Layer also can be colored, and improves the decorative effect of metal.B. the hardness of oxide-film is high, and the hardness of anode oxide film is the highest, its hardness
About at 196-490HV, because the wearability that hardness height determines oxide-film is the best.C. the corrosion resistance of oxide-film, aluminum oxidation
Film is the most stable in air, soil, and the adhesion with matrix is the strongest, generally all can carry out the sealing of hole that dyes after oxidation
Or spray treatment so that it is corrosion resistance further enhances.D. the adhesion of oxide-film, oxidation oxide-film is in the combination of parent metal
Power is very strong, and they are separated by the method for very difficult machinery, even if film layer is with metal bending, film layer still keeps good in parent metal
Combination, but the plasticity of oxide-film is little, and fragility is big, when film layer is by bigger impact load and flexural deformation, can produce Testudinis
Split, so this oxide-film is difficult to use under mechanical action, can serve as the bottom of skin of paint.
The physical or chemical treatment process after alumilite process, oxide-film carried out, with reduce oxide-film porosity and
Absorbability, in order to dyestuff is sealed in micropore, improves the corrosion resistance of film, the performance such as wear-resisting simultaneously.In the building trade world
Various countries substantially use high-temperature steam method, cold seal hole, three kinds of techniques of electrophoretic deposition to the sealing of hole of oxide-film, but current middle temperature is sealed
There is the trend of expansion in hole.Divide from sealing of hole principle and mainly have hydration reaction, inorganics filled or Organic substance filling three major types.Heat-sealing
Hole technique includes: a. boiling water sealing hole: in the pure water of boiling point (temperature more than 95 degree, deionized water), pass through aluminium oxide
Hydration reaction amorphous aluminium oxide is changed into hydrated alumina, due to volume that aqua oxidation aluminum ratio is original big 30%,
The micropore filling of the oxide-film that volumetric expansion makes is closed.B. high-temperature steam sealing of hole: principle is the same with boiling water sealing hole, advantage: speed
Hurry up, the dependency of water quality is little, occur that white lime, risk of fading are little less.
CN103215630A discloses a kind of method that aluminium alloy anode oxide film hole closed by inorganic-organic composite silicon colloidal sol,
It is that the aluminum or aluminum alloy anode surface after pre-treatment is coated or the organic inorganic compounding silica sol layer of deposited overlayers, then warp
Dry, sintering is made.Described organo-mineral complexing Ludox is by 0.5-30ml silane reagent or tetraethyl orthosilicate, 0.5-
30ml inorganic silicon solution, 1-40ml water, 1-90ml organic solvent, 0.05-100g filler powder body and 0.01-10g surfactant
Make.CN103343374B discloses the hard anodizing processing method of a kind of cast aluminium alloy workpiece, closes including by aluminum silicon cast aluminium
After gold is melted, injects in die casting machine and carry out die cast, obtain corresponding cast aluminium alloy workpiece;Then, by above-mentioned cast aluminium alloy work
Part carries out heat treatment under conditions of 350 DEG C~450 DEG C;Finally, the cast aluminium alloy workpiece after Overheating Treatment is carried out hard
Anodized, makes to form horniness anode oxide film at cast aluminium alloy surface of the work.But above-mentioned processing method obtains
Aluminium alloy remains the problem that corrosion resistance is bad.
Summary of the invention
It is an object of the invention to: a kind of method that aluminum alloy surface is carried out anodic oxidation sealing treatment, the method are provided
Aluminium alloy after process has excellent decay resistance.
Technical scheme is:
The processing method of a kind of aluminum alloy surface anodic oxidation-sealing of hole, comprises the steps:
1st step, the surface preparation to aluminium alloy;
2nd step, the aluminium alloy obtaining the 1st step forms oxide-film by anodic oxidation in the electrolytic solution, described electrolyte
Composition is sulphuric acid 130~160g/L, Nano-meter SiO_221~6g/L, water-borne acrylic resin 0.5~2g/L and cerous nitrate 0.5~
2g/L;
3rd step, the aluminium alloy after processing the 2nd step carries out sealing treatment, the first confining liquid of employing for the first time in enclosed slot
Composition be: citric acid 2~5g/L, chromic nitrate 2~3g/l, tertiary sodium phosphate 0.4~0.8g/l, EDTA-Na20.5~0.8g/
L, nickel sulfate 0.02~0.04g/l;
4th step, the aluminium alloy after processing the 3rd step carries out second time sealing treatment, and the composition of the second confining liquid of employing is: water
Property acrylic resin 40~45g/l, nonionic surfactant 0.5~1g/l, Nano-meter SiO_228~12g/l, secondary octyl phenol gathers
Oxygen vinyl Ether 3~5g/l;
5th step, then after washing, air-drying process, obtain aluminium alloy.
In the 1st described step, pretreatment refers to one or several in polishing, oil removing fat.
In the 1st described step, aluminium alloy can be cast aluminium alloy ZL101, ZL102, ZL105, ZL105A, ZL107,
ZL110 or ZL108.
In the 2nd described step, anodised technological parameter is: temperature :-4~4 DEG C, electric current density: 2.4~3.7A/
cm2, voltage: 42~50V, the time: 20~30min.
In the 3rd described step, the parameter of " locked in " operation is: temperature: 30~40 DEG C, the time: 30~50min.
In the 4th described step, the parameter of " locked in " operation is: temperature: 20~30 DEG C, the time: 4~7min.
The described Nano-meter SiO_2 in the 2nd step2Refer to the SiO through hydroxyl silicon oil modified mistake2, modification procedure is:
1000mL four-neck flask adds 40g sodium silicate, 6g sodium sulfate and 466mL water, at 30 DEG C, stirs 30min, be warming up to 85 DEG C,
Sulfuric acid solution to system pH of dropping 12wt% is 10.5, is aged 20min.Add 12wt% sulphuric acid and adjust pH to 4.7, add hydroxyl silicon
Oil 40g, after stirring 1h, is aged 1.5h.Filtering, filter cake is through being washed in washing liquid without SO4 2-, washing with alcohol removes moisture, is dried
The SiO of hydroxyl silicon oil modified mistake2。
Beneficial effect
The aluminium alloy that the processing method of the present invention obtains processes through anodic oxidation, closed for second time, has corrosion resistance and good
Advantage.
Detailed description of the invention
Embodiment 1
1st step, surface finish, the oil removing fat pretreatment to cast aluminium alloy ZL101;
2nd step, the aluminium alloy obtaining the 1st step forms oxide-film by anodic oxidation in the electrolytic solution, described electrolyte
Composition is sulphuric acid 130g/L, Nano-meter SiO_221g/L, water-borne acrylic resin 0.5g/L and cerous nitrate 0.5g/L;Anodised
Technological parameter is: temperature :-4 DEG C, electric current density: 2.4A/cm2, voltage: 42V, time: 20min;
3rd step, the aluminium alloy after processing the 2nd step carries out sealing treatment, the first confining liquid of employing for the first time in enclosed slot
Composition be: citric acid 2g/L, chromic nitrate 2g/l, tertiary sodium phosphate 0.4g/l, EDTA-Na20.5g/l, nickel sulfate 0.02g/l;
The parameter of " locked in " operation is: temperature: 30 DEG C, time: 30min;
4th step, the aluminium alloy after processing the 3rd step carries out second time sealing treatment, and the composition of the second confining liquid of employing is: water
Property acrylic resin 40g/l, nonionic surfactant 0.5g/l, Nano-meter SiO_228g/l, secondary octyl phenol polyethenoxy ether 3g/
l;The parameter of " locked in " operation is: temperature: 20 DEG C, time: 4min.
5th step, then after washing, air-drying process, obtain aluminium alloy.
Embodiment 2
1st step, surface finish, the oil removing fat pretreatment to cast aluminium alloy ZL101;
2nd step, the aluminium alloy obtaining the 1st step forms oxide-film by anodic oxidation in the electrolytic solution, described electrolyte
Composition is sulphuric acid 160g/L, Nano-meter SiO_22 6g/L, water-borne acrylic resin 2g/L and cerous nitrate 2g/L;Anodised technique is joined
Number is: temperature: 4 DEG C, electric current density: 3.7A/cm2, voltage: 50V, time: 30min;
3rd step, the aluminium alloy after processing the 2nd step carries out sealing treatment, the first confining liquid of employing for the first time in enclosed slot
Composition be: citric acid 5g/L, chromic nitrate 3g/l, tertiary sodium phosphate 0.8g/l, EDTA-Na20.8g/l, nickel sulfate 0.04g/l;Envelope
The parameter of closed operation is: temperature: 40 DEG C, time: 50min;
4th step, the aluminium alloy after processing the 3rd step carries out second time sealing treatment, and the composition of the second confining liquid of employing is: water
Property acrylic resin 45g/l, nonionic surfactant 1g/l, Nano-meter SiO_2212g/l, secondary octyl phenol polyethenoxy ether 5g/l;
The parameter of " locked in " operation is: temperature: 30 DEG C, time: 7min.
5th step, then after washing, air-drying process, obtain aluminium alloy.
Embodiment 3
1st step, surface finish, the oil removing fat pretreatment to cast aluminium alloy ZL101;
2nd step, the aluminium alloy obtaining the 1st step forms oxide-film by anodic oxidation in the electrolytic solution, described electrolyte
Composition is sulphuric acid 140g/L, Nano-meter SiO_222g/L, water-borne acrylic resin 0.8g/L and cerous nitrate 1g/L;Anodised work
Skill parameter is: temperature: 2 DEG C, electric current density: 2.8A/cm2, voltage: 48V, time: 25min;
3rd step, the aluminium alloy after processing the 2nd step carries out sealing treatment, the first confining liquid of employing for the first time in enclosed slot
Composition be: citric acid 4g/L, chromic nitrate 2g/l, tertiary sodium phosphate 0.6g/l, EDTA-Na20.6g/l, nickel sulfate 0.02g/l;
The parameter of " locked in " operation is: temperature: 35 DEG C, time: 35min;
4th step, the aluminium alloy after processing the 3rd step carries out second time sealing treatment, and the composition of the second confining liquid of employing is: water
Property acrylic resin 42g/l, nonionic surfactant 0.8g/l, Nano-meter SiO_2210g/l, secondary octyl phenol polyethenoxy ether 4g/
l;The parameter of " locked in " operation is: temperature: 25 DEG C, time: 6min.
5th step, then after washing, air-drying process, obtain aluminium alloy.
Embodiment 4
Difference with embodiment 3 is: the described Nano-meter SiO_2 in the 2nd step2Refer to the SiO through hydroxyl silicon oil modified mistake2, change
Property step be: in 1000mL four-neck flask, add 40g sodium silicate, 6g sodium sulfate and 466mL water, at 30 DEG C, stir 30min,
Being warming up to 85 DEG C, sulfuric acid solution to system pH of dropping 12wt% is 10.5, is aged 20min.Add 12wt% sulphuric acid and adjust pH extremely
4.7, add hydroxy silicon oil 40g, after stirring 1h, be aged 1.5h.Filtering, filter cake is through being washed in washing liquid without SO4 2-, washing with alcohol
Remove moisture, be dried to obtain the SiO of hydroxyl silicon oil modified mistake2。
1st step, surface finish, the oil removing fat pretreatment to cast aluminium alloy ZL101;
2nd step, the aluminium alloy obtaining the 1st step forms oxide-film by anodic oxidation in the electrolytic solution, described electrolyte
Composition is sulphuric acid 140g/L, the Nano-meter SiO_2 of hydroxyl silicon oil modified mistake22g/L, water-borne acrylic resin 0.8g/L and cerous nitrate
1g/L;Anodised technological parameter is: temperature: 2 DEG C, electric current density: 2.8A/cm2, voltage: 48V, time: 25min;
3rd step, the aluminium alloy after processing the 2nd step carries out sealing treatment, the first confining liquid of employing for the first time in enclosed slot
Composition be: citric acid 4g/L, chromic nitrate 2g/l, tertiary sodium phosphate 0.6g/l, EDTA-Na20.6g/l, nickel sulfate 0.02g/l;
The parameter of " locked in " operation is: temperature: 35 DEG C, time: 35min;
4th step, the aluminium alloy after processing the 3rd step carries out second time sealing treatment, and the composition of the second confining liquid of employing is: water
Property acrylic resin 42g/l, nonionic surfactant 0.8g/l, Nano-meter SiO_2210g/l, secondary octyl phenol polyethenoxy ether 4g/
l;The parameter of " locked in " operation is: temperature: 25 DEG C, time: 6min.
5th step, then after washing, air-drying process, obtain aluminium alloy.
Process on Aluminum Alloy Oxidation Film barrier propterty is tested, using untreated cast aluminium alloy ZL101 as comparison.
Artificial atmosphere corrosion testing salt spray test (GB/T10125-2012);Copper accelerated acetic acid salt spray test (GB/
T12967.3-2008) ;Cyclic damp heat test (GJB150.9-86);Mould test (GJB150.10-86);1h100 DEG C of high temperature
Test (GJB150.3-86).
In form, the time of statistics is time when there is a naked eyes visible change on surface occur.
As can be seen from the table, the aluminium alloy surface treatment method of the present invention can improve the decay resistance on surface, logical
Cross after the silicon oxide in anodic oxidation is modified, can improve and the compatibility of the confining liquid in closing, improve and close
Effect, reaches to improve the purpose of decay resistance.