CN1670263A - Anodizing method for generating ceramic film on aluminium and its alloy material surface - Google Patents
Anodizing method for generating ceramic film on aluminium and its alloy material surface Download PDFInfo
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Abstract
The invention relates to an anodizing method for generating ceramic film on aluminium and its alloy material surface, which comprises placing aluminum and its alloy material in certain composite electrolytic solution, employing high unidirectional or controlled asymmetrical oxidization voltage under the condition of arc-suppressing but no spark discharge, subjecting aluminum and its alloy to electrochemical ceramic film forming treatment, producing an Al2O3 ceramic film on the surface of aluminum and its alloys.
Description
Technical field:
The present invention relates to the anodizing method that a kind of aluminium and alloy surface thereof generate ceramic membrane.
Background technology:
Aluminium and alloy material thereof are widely used in the every field of national economy owing to characteristics such as its excellent physics, chemistry, mechanical property and light specific gravity, easy processing.Yet because the aluminum alloy surface difference of hardness, the standard equilibrium potential is easy to be subjected to the corrosion and the wearing and tearing of environment than bearing, thereby aluminum alloy spare part often will carry out suitable surface treatment before use.The process for treating surface of aluminum current alloy mainly is anonizing and chemical oxidization method.
Can generate one deck through the aluminium of general chemistry or electrochemical method oxidation and alloy surface thereof and have certain degree of hardness (200～300HV) and the oxide film of certain corrosion resistance nature, after the anode oxide film with porous layer and barrier layer structure being proceeded the processing of chemistry or electrochemical coloring, the common anode oxide film has good decorate properties.Thereby this surface treatment method is used widely in fields such as architectural aluminum section, aluminium base five metals household electrical appliances.Yet, along with the continuous development and the aluminum base alloy of national economy is applied even more extensively in the civilian industry of space flight and aviation, defence and military, automobile mechanical and light industry, more and more higher and more and more various property to the aluminum alloy surface performance demands, for example: require aluminum alloy material surface to have higher hardness (more than the 400HV) and wear resistance; Require the aluminium surface film oxide to have alkali resistance and acid resistance preferably; Require the surface to have excellent decorate properties simultaneously.The present invention is just under the background of a kind of like this technology and market demands, adopt the electrochemical anodic oxidation technology to make aluminium and alloy material thereof in a kind of solution that contains composite electrolytic solution, it is 400～800HV that the surface generates one deck microhardness rapidly, the wear and corrosion behavior excellence has the ceramic membrane of bright-coloured color and excellent decorate properties simultaneously.The present technique component both had been different from the conventional anodic oxidation of aluminium, also was different from micro-arc anodic oxidation, was a kind of brand-new aluminium process for treating surface.
Adopt higher asymmetric pulsation voltage and rush current that aluminium and alloy surface thereof are generated the ceramic membrane method, the more of usefulness mainly is the differential arc oxidation method at present.Chinese patent publication number 1262344,1115793 etc. has proposed plasma and has strengthened electrochemical surface potteryization method, this technology mainly produces the plasma body arc discharge by the surface at metallic matrix and electrolytic solution, makes the surface form one deck sedimentation type ceramic coating.The principal character of oxidising process is that electrode/solution interface can produce intensive arc discharge phenomenon, and its electrolytic solution is based on polyphosphoric acid salt.Publication number 1163323 has proposed a kind of plasma and has strengthened energy control method in the electrochemical surface ceramic treatment process.Publication number 1163324 has proposed to adopt after the ceramic treatment electrophoretic painting to strengthen the wear resistance and the weathering resistance of single film, has widened the Application Areas of metal ceramic film.Have certain solidity to corrosion and better ornamental rete though aforesaid method can form one deck in the metallic surface, the hardness of rete and wear resisting property are not high, often can only use as the middle layer of filming.
Summary of the invention:
Purpose of the present invention has aimed to provide and a kind ofly can under the flashing discharge condition, not make aluminium and alloy surface thereof generate the anodizing method of one deck high rigidity, abrasion resistant and corrosion resistant and excellent decorate properties ceramic film fast in lower energy consumption.
The present invention is by the following technical solutions:
With aluminium or its alloy material as anode, place composite electrolytic solution, adopt unidirectional or controlled asymmetric oxidation voltage, control voltage was raised to required voltage 80V～300V from 0V in 20～120 seconds, and remain unchanged, until end, oxidation current raises with voltage and increases, and reaches peak current density 5～30A/dm
2After, descend rapidly, finish until film forming; Oxidation is carried out under no arc sparkless discharge all the time; Described composite electrolytic solution composition comprises organic carboxyl acid and derivative thereof, inorganic phosphorated, boron-containing compound, and the metal oxygen-containing hydrochlorate, the composite electrolyte total concn is: 5～100g/L.
Voltage waveform can adopt unidirectional pulse, asymmetrical alternating current or asymmetry pulse.Described voltage can be 100V～200V, peak current density 5～12A/dm
2, electrolyte temperature is 5～65 ℃.When current density is finally reduced to 1～2A/dm
2, then film forming finishes.
Sustainable 5～10 seconds of described peak point current.
Oxidation of the present invention is under the no arc sparkless discharging condition all the time to be carried out, and under the condition that adopts the oxidation of alternation ripple voltage, the aluminium surface can have fluorescence to occur slightly, and separate out with oxygen all the time on the aluminium surface in the oxidising process.
Described organic carboxyl acid and derivative thereof are the organic di-carboxylic acid that contains 2～8 carbon atoms; Can be propanedioic acid, Succinic Acid, lactic acid, tartrate, toxilic acid, citric acid, oxalic acid etc.
Described inorganic phosphorated, boron compound is phosphorous or contains acid and potassium, sodium or the ammonium salt of boron; Can be phosphoric acid, tetra-sodium, polyphosphoric acid, phosphoric acid salt, pyrophosphate salt, polyphosphoric acid salt, boric acid, metaboric acid, tetraborate etc.
Described metal oxygen-containing hydrochlorate is that vanadium, tungsten or molybdenum combine the simple salt that forms with oxygen, and aqueous solution formula of is N
2OMO
3NH
2O, wherein N is K
+, Na
+, NH
4 +, M is the corresponding metal element, n is the number of crystal water.Can be vanadate, tungstate, aluminate etc.
Because arc discharge does not take place in oxidising process of the present invention, what adopt is higher pulsed voltage and rush current, make aluminium and alloy surface thereof form the ceramic membrane zone of oxidation of one deck high rigidity, abrasion resistant and corrosion resistant and excellent decorate properties fast, its Production Flow Chart is identical with the common anode oxidation:
Degreasing → washing → but arc electrochemistry pottery film forming → washing → oven dry
The present invention becomes assignment system because of the color and luster to product requires difference different, generally is divided into following four kinds:
(1) canescence series ceramic film forming anodizing
Canescence series ceramic film forming anodizing electrolytic solution mainly contains organic carboxyl acid and derivative thereof as oxalic acid: 1.0～6.0g/L, Succinic Acid: 0.5～2.5g/L; Inorganic phosphorated, boron compound is as phosphoric acid 5～10ml/L, boric acid 5～20g/L, phosphoric acid salt 0.5～10g/L; The metal oxygen-containing hydrochlorate is as compositions such as vanadate 0.5～10g/L, tungstate 0.5～10g/L.Organic carboxyl acid is main filmogen, and inorganic phosphorated, boron compound and metal oxygen-containing hydrochlorate have the film forming of raising current density, accelerate voltage change, evenly the effect of rete.
The CONTROL PROCESS condition: control voltage was raised to required voltage from 0V in 20～120 seconds (80V～300V), and remaining unchanged is until off-test.Oxidation current raises with voltage and increases, and reaches peak current density (5～30A/dm
2) after, continue 5-10 after second, descend rapidly, finally reduce to 1～2A/dm
2Oxidization time: 5～30min.Temperature: 5～65 ℃.
(2) Yellow series pottery film forming anodizing
The rete that this kind system obtains all is Yellow series retes, and electrolytic solution mainly contains organic carboxyl acid and derivative thereof as oxalic acid: 8～15g/L, lactic acid: 2～10ml/L.Inorganic phosphorated, boron compound is as pyrophosphate salt: 10～15g/L, tetra-sodium: 1～4ml/L, boric acid: 5～20g/L.The metal oxygen-containing hydrochlorate is as molybdate: 0.5～5g/L, tungstate: compositions such as 0.5～10g/L.The effect of each component of electrolytic solution is the same, and the color of oxide film is mainly by concentration decision inorganic phosphorated, boron compound.The CONTROL PROCESS condition is the same.
(3) grey series ceramic film forming anodizing
What this kind component carried out that pottery changes into that film obtains mainly is the rete of grey color system, electrolytic solution mainly contain organic carboxyl acid and derivative thereof as: tartrate is: 8～25g/L, citric acid is: 5～10g/L.Inorganic phosphorated, boron compound is as tetra-sodium: 1～5ml/L, polyphosphoric acid: 2～8ml/L, sodium polyphosphate: 10～15g/L, metaboric acid: 0.5～5g/L, sodium tetraborate: 10～25g/L.The metal oxygen-containing hydrochlorate as: vanadate 0.5～2.0g/L, tungstate is: compositions such as 0.5～10g/L.The effect of each component of electrolytic solution is the same, and its rete color is mainly determined by the concentration of organic carboxyl acid.The CONTROL PROCESS condition is the same.
(4) black series ceramic film forming anodizing
What this system electrolyte component carried out that pottery changes into that film obtains mainly is atropurpureus series rete, electrolytic solution mainly contain organic carboxyl acid as: toxilic acid is: 0.5～10g/L, propanedioic acid is: 1.0～2.0g/L.Inorganic phosphorated, boron compound as: tetra-sodium is: 1～5ml/L, polyphosphoric acid is: 2～8ml/L, sodium polyphosphate is: 10～15g/L, metaboric acid: 0.5～5g/L, sodium tetraborate is: 10～15g/L.The metal oxygen-containing hydrochlorate as: molybdate is: 0.5～4.0g/L, vanadate is: compositions such as 0.5～10g/L.The effect of each component of electrolytic solution is the same, and its rete color is mainly determined by the concentration of organic carboxyl acid.The CONTROL PROCESS condition is the same.
The present invention adopts the electrolytic solution of above-mentioned different colours system to carry out anodizing, aluminium is in this specific electrolyte solution, under the effect of ripple voltage, dissolving rapidly takes place in the surface, the dissolved aluminum ion forms gluey flocbed at electrode/solution interface and metal oxygen-containing acid anion and organic carboxyl acid negatively charged ion, and along with dissolved constantly carries out, flocbed is constantly thickeied, simultaneously because the effect of the huge interface Jiao Erre that high ripple voltage and anodic current produce, flocbed takes place to concentrate, dehydration, the final ceramic membrane zone of oxidation that forms with nanostructure.Heat-tinting one step finishes, the rete lovely luster, the porcelain sense is strong, can form canescence, yellow, brown, purple is serial, has extraordinary ornamental.The rete microhardness can reach 400～800HV, the wear and corrosion behavior excellence, and have excellent acid and alkali-resistance and chemical solvents performance, can reach durable in use.
The difference of the present invention and plasma intensified electrochemical surface potteryization method maximum just is can not discharge by flashing in the film process, be fit to the safety in production standard, and current density descends along with film forming carrying out, average energy consumption is less, the rete that obtains not only has excellent decorate properties and well anti-corrosion and wear resisting property is arranged, and can be used for outermost layer and decorate and the protective rete.
Electrolytic solution of the present invention is for adopting the novel anodizing composite electrolytic solution of development voluntarily, and its oxidation electrolyte concentration is lower, solution nontoxicity, non-corrosiveness, environmentally safe.The developing direction that meets the environmental protection industry.
Anode oxidation process of the present invention is simple, and it is constant that electrolyte temperature need not to keep, can be 5～65 ℃ of range; Anodic oxidation can be controlled in 5～15min and finishes; The average formation speed of rete can reach 3～5 μ m/min; Thicknesses of layers can change between 10～50 μ m, after film forms, can carry out using after sealing of hole is handled and also can directly use.
An anode oxidation film-forming and a painted step finish, and the ceramic coating microhardness that is generated can reach 400～800HV; Alkali resistance (titration of 10%NaOH solution) can reach more than the 10min.But series ceramic gloss such as rete gray, brown, yellow and black, the decorate properties with excellence.Ceramic membrane surface has the aperture that diameter is 100～200nm, and hole density is about 10/μ m
2, the film cross section is the mesh nanometer structure.
Nontoxic, the non-corrosiveness of anodizing electrolyte solution composition of the present invention, environmentally safe belongs to green process for treating surface.Press down arc electrochemistry pottery film forming process, have characteristics such as plant and instrument less investment, production technique is simple, the one-pass film-forming area is big, tooling cost is low, and has an excellent decoration performance, in case product adopts present technique as its process for treating surface, to improve added value of product greatly, and make product have the stronger market competitiveness.
Embodiment
Embodiment 1:
Utilize present embodiment and tooling cost estimation explanation the present invention below,
1, starting material
(a pot mouthful diameter is 20cm to ordinary pan, and the bottom of a pan diameter is 21cm, is 9cm highly, and the total area is about 24dm with antirust aluminum component
2)
2, the pre-treatment of test specimen
Degreasing → washing → but arc electrochemistry pottery film forming → washing → oven dry
The aluminum component that extruding is come out must carry out oil removing degreasing pre-treatment, and whether pre-treatment thoroughly has very big influence to film forming properties.If pre-treatment is not thorough, when carrying out oxidation,, can not form the successive ceramic film on the test specimen surface because the grease of absorption will change the electrochemical behavior at aluminium/electrolyte solution interface, thereby cause under high-voltage, big electric current, violent spot corrosion taking place become very coarse of specimen surface.
3, electrolyte component determines
According on the pressure kettle spare canescence ceramic film being required and the demand in market, we select following canescence potteryization components system for use:
Organic carboxyl acid: oxalic acid: 5.0g/L, Succinic Acid: 2.0g/L.
Inorganic phosphorated, boron-containing compound: phosphoric acid: 8ml/L, boric acid: 20g/L, phosphoric acid salt: 6g/L.
Metal oxygen-containing hydrochlorate: tungstate: 5.0g/L, vanadate; 1.0g/L.
During obtain solution, earlier with deionized water with medicine all dissolving make concentrated solution, wiring solution-forming in oxidation trough as required then.Solution can heat up in the film forming process of electrochemistry pottery and volatilize, and note make-up solution timely.
4, pressing down arc electrochemistry pottery film-forming process handles
With the workpiece ceramic treatment system of packing into, the control anodizing voltage rises to 150 volts by 0 volt in 30s, and oxidation current increases with the voltage rising, reaches peak current density 12A/dm
2, and continue 6 seconds, and allow film forming carry out automatically then, finish (in the operating process, until film forming when current density drops to 2A/dm
2During the left and right sides, think that then film process finishes).Can also control film formation time to the requirement of thickness according to the client equally, be generally 5～10min, the time, longer rete was also thicker.Solution temperature need not forced refrigeration, only needs to adopt the recirculated cooling water cooling that tank liquor is not seethed with excitement and gets final product.
5, chemical process tooling cost estimation
Electrochemical production aluminium surface multifunctional ceramic composite film technology and conventional anodic oxidation or differential arc oxidation electrolytic process are all inequality, groove is pressed basic constant, the slightly rising that keeps in this achievement anodizing course of processing, and Faradaic current raises (soft start) with anode voltage at first and increases rapidly, voltage reaches prevalue, electric current reaches peak value, current density is index decreased in time subsequently, drops at last＜1A/dm
2, oxidation finishes.It is 100～180V that the average groove of oxidation system that general this achievement provides is pressed, and average current density is 3～6A/dm
2, average film formation time is 5～10 minutes, the energy consumption (ρ) that can calculate preparation unit surface ceramic film thus is:
ρ
Minimum=I
Minimum* V
Minimum* t
Minimum=3 * 100 * 5 * 60=90 * 10
3J/dm
2
ρ
Maximum=I
Maximum* V
Maximum* t
Maximum=6 * 180 * 10 * 60=648 * 10
3J/dm
2
Annotate: because of the system difference, rete is required difference, and the electrolysis mode of selecting is different with parameter.Therefore the energy consumption of unit surface ceramic film is at ρ
MinimumAnd ρ
MaximumBetween change.
Compare with sulfuric acid, oxalic acid system aluminium hard anodizing, the average groove of hard anodizing is pressed and is 40V (phenomenon of boosting), and current density is 2.5A/dm
2, oxidization time is 60 minutes.
ρ
Hard=40 * 2.5 * 60 * 60=360 * 10
3J/dm
2
This shows ρ
Minimum＜ρ
Hard＜ρ
Maximum
Below only give comparison from oxidation voltage and current density angle, in fact during the aluminium alloy hard anodizing electrolyte temperature general requirement be controlled at≤0 ℃, therefore the hard anodizing system is wanted the huge refrigerating apparatus system of investment buying, and will expend a large amount of energy for keeping electrolytic condition.And the preparation process of electrochemical function ceramic film need not be kept electrolyte temperature especially, as long as keep electrolyte temperature＜60 ℃, a large amount of volatilizations do not take place and get final product in solution, therefore do not need to install special refrigerator and temperature controlling system, only need utilize recirculating cooling water system (tube bank) can satisfy the production needs.
The energy expenditure of to sum up analyzing process unit's area function ceramic membrane often will be lower than the energy expenditure of unit hard anodic oxidation coating.
Embodiment 2:
Starting material are the same; The pre-treatment of test specimen is the same; Determining of bath composition
According on the pressure kettle spare yellow ceramic film being required and the demand in market, we select for use following yellow to press down arc electrochemistry potteryization components system:
Organic carboxyl acid and derivative thereof: oxalic acid: 8g/L, lactic acid: 5ml/L.
Inorganic phosphorated, boron compound: pyrophosphate salt: 12g/L, tetra-sodium: 3ml/L, boric acid: 15g/L.
Metal oxygen-containing hydrochlorate: molybdate: 2g/L, tungstate: 5g/L.
Pressing down arc electrochemistry pottery film forming handles
With the workpiece ceramic treatment system of packing into, the control anodizing voltage rises to 130 volts by 0 volt in 30s, and oxidation current increases with the voltage rising, reaches peak current density 10A/dm
2, and continue 8 seconds, and allow film forming carry out automatically then, finish (in the operating process, until film forming when current density drops to 2A/dm
2During the left and right sides, think that then film process finishes).Can also control film formation time to the requirement of thickness according to the client equally, be generally 5～10min, the time, longer rete was also thicker.Solution temperature need not forced refrigeration, only needs to adopt the recirculated cooling water cooling that tank liquor is not seethed with excitement and gets final product.
Embodiment 3
The CONTROL PROCESS condition: control voltage was raised to required voltage 100V from 0V in 20 seconds, and remained unchanged, until off-test.Oxidation current raises with voltage and increases, and reaches peak current density 6A/dm
2After, and continue 10 seconds, and descend rapidly, finally reduce to 1～2A/dm
2Oxidization time: 10min.Temperature: 5～65 ℃.
Following table has reflected the influence to film performance of organic carboxyl acid concentration such as oxalic acid.Other composition of electrolyte solution: Succinic Acid: 2.0g/L, phosphoric acid: 6ml/L, boric acid 10g/L, phosphoric acid salt 8g/L, vanadate 8g/L, tungstate 5g/L.
Table 1
| Concentration of oxalic acid (g/L) | Outward appearance | Thickness (μ m) | Hardness (HV) |
| ????1.0 ????2.0 ????4.0 ????6.0 | The greyish white palm fibre ash of light gray | ??45 ??27 ??21 ??25 | ????405 ????507 ????565 ????492 |
Embodiment 4
That following table has been listed is inorganic phosphorated, boron compound concentration is to the ceramic film Effect on Performance.Other composition of electrolyte solution: oxalic acid: 12g/L, lactic acid: 8ml/L, pyrophosphate salt: 10g/L, tetra-sodium: 2ml/L, molybdate: 2g/L, tungstate: 5g/L
Table 2
| Boric acid concentration (g/L) | Color | Thickness (μ m) | Hardness (HV) |
| ???10 ???15 ???20 | Sallow sallow sallow | ???19 ???17 ???10 | ????502 ????480 ????390 |
The CONTROL PROCESS condition is with embodiment 1.
Embodiment 5
Following table has been listed the influence to film performance of organic carboxyl acid such as tartaric acid concentration.Other composition of electrolyte solution: citric acid is: 5g/L, tetra-sodium: 2ml/L, polyphosphoric acid: 2ml/L, sodium polyphosphate: 12g/L, metaboric acid: 1.5g/L, sodium tetraborate: 15g/L, vanadate 1.5g/L, tungstate: 5g/L.
Table 3
| Tartrate (g/L) | Outward appearance | Thickness (μ m) | Hardness (HV) |
| ????10 ????12 ????14 ????16 | Dull gray is grayish green dark-grey | ????26 ????27 ????23 ????20 | ????516 ????472 ????448 ????494 |
The CONTROL PROCESS condition is with embodiment 1.
Embodiment 6
Following table has been represented the influence to film performance of organic carboxyl acid such as toxilic acid concentration.Other composition of electrolyte solution: propanedioic acid: 1.5g/L, tetra-sodium: 2ml/L, polyphosphoric acid: 6ml/L, sodium polyphosphate: 12g/L, metaboric acid: 2.0g/L, sodium tetraborate: 15g/L, molybdate: 2g/L, vanadate: 5g/L.。The CONTROL PROCESS condition is with embodiment 1.
Table 4
| Toxilic acid (g/L) | Color | Thickness (μ m) | Hardness (HV) |
| ????0.5 ????2.0 ????3.0 ????5.0 | The purple black purple black look of brown | ????39 ????30 ????32 ????21 | ????501 ????661 ????588 ????610 |
The above embodiment of the invention only be implementation process and and non-limiting the present invention.
Claims (10)
1, a kind of aluminium and alloy material thereof surface generates the anodizing method of ceramic membrane, it is characterized in that: with aluminium or its alloy material as anode, place composite electrolytic solution, adopt unidirectional or controlled asymmetric oxidation voltage, control voltage was raised to required voltage 80V～300V from 0V in 20～120 seconds, and remain unchanged, oxidation current raises with voltage and increases, and reaches peak current density 5～30A/dm
2After, descend rapidly, finish until film forming, oxidation is carried out under no arc sparkless discharge all the time; Described composite electrolytic solution composition comprises organic carboxyl acid and derivative thereof, inorganic phosphorated, boron-containing compound, and the metal oxygen-containing hydrochlorate, the composite electrolyte total concn is: 5～100g/L.
2, a kind of aluminium according to claim 1 and alloy material thereof surface generates the anodizing method of ceramic membrane, it is characterized in that: voltage waveform can adopt unidirectional pulse, asymmetrical alternating current or asymmetry pulse, magnitude of voltage 100V～200V, peak current density 5～12A/dm
2, electrolyte temperature is 5～65 ℃.
3, a kind of aluminium according to claim 1 and 2 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: oxidation is under the no arc sparkless discharging condition all the time to be carried out, and oxidation voltage adopts the alternation ripple voltage.
4, a kind of aluminium according to claim 1 and 2 and alloy material thereof surface generates the anodizing method of ceramic membrane, it is characterized in that: peak point current continues 5～10 seconds.
5, a kind of aluminium according to claim 1 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: organic carboxyl acid and derivative thereof are the organic di-carboxylic acid that contains 2～8 carbon atoms; Inorganic phosphorated, boron compound is phosphorous or contains the acid and the k-na salt thereof of boron; The metal oxygen-containing hydrochlorate is that vanadium, tungsten or molybdenum combine the simple salt that forms with oxygen, and aqueous solution formula of is N
2OMO
3NH
2O, wherein N is K
+, Na
+, NH
4 +, M is the corresponding metal element, n is the number of crystal water.
6, a kind of aluminium according to claim 5 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: organic carboxyl acid and derivative thereof are propanedioic acid, Succinic Acid, lactic acid, tartrate, toxilic acid, citric acid, oxalic acid; Inorganic phosphorated, boron compound is phosphoric acid, tetra-sodium, polyphosphoric acid, phosphoric acid salt, pyrophosphate salt, polyphosphoric acid salt, boric acid, metaboric acid, tetraborate; The metal oxygen-containing hydrochlorate is vanadate, tungstate, molybdate.
7, a kind of aluminium according to claim 1 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: composite electrolytic solution is oxalic acid: 1.0～6.0g/L, Succinic Acid: 0.5～2.5g/L; Phosphoric acid 5～10ml/L, boric acid 5～20g/L, phosphoric acid salt 0.5～10g/L; Vanadate 0.5～10g/L, tungstate 0.5～10g/L.
8, a kind of aluminium according to claim 1 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: composite electrolytic solution is oxalic acid: 8～15g/L, lactic acid: 2～10ml/L; Pyrophosphate salt 10～15g/L, tetra-sodium: 1～4ml/L, boric acid: 5～20g/L; Molybdate: 0.5～5g/L, tungstate: 0.5～10g/L.
9, a kind of aluminium according to claim 1 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: composite electrolytic solution is tartrate: 8～25g/L, citric acid: 5～10g/L; : tetra-sodium: 1～5ml/L, polyphosphoric acid: 2～8ml/L, sodium polyphosphate: 10～15g/L, metaboric acid 0.5～5g/L, sodium tetraborate 10～25g/L; Vanadate 0.5～2.0g/L, tungstate: 0.5～10g/L.
10, a kind of aluminium according to claim 1 and alloy material thereof surface generates the anodizing method of ceramic membrane, and it is characterized in that: composite electrolytic solution is toxilic acid: 0.5～10g/L, propanedioic acid: 1.0～2.0g/L; Tetra-sodium: 1～5ml/L, polyphosphoric acid: 2～8ml/L, sodium polyphosphate: 10～15g/L, metaboric acid 0.5～5g/L, sodium tetraborate: 10～15g/L; Molybdate: 0.5～4.0g/L, vanadate: 0.5～10g/L.
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