CN108914184B - A kind of low energy consumption aluminum alloy differential arc oxidation film layer preparation method - Google Patents
A kind of low energy consumption aluminum alloy differential arc oxidation film layer preparation method Download PDFInfo
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Abstract
The invention discloses a kind of aluminum alloy differential arc oxidation film layer preparation method of low energy consumption, preparation process includes pre-treatment, four part of anodized, electrolytic deposition and micro-arc oxidation treatment.Pre-treatment is to be polished aluminium alloy, polished, cleaned, alkaline etching, pickling, cleaning and dried up.Sample after pre-treatment, it is deposited using DC anodizing and alternating current electrolysis, form the anode oxide film for having nano-metal particle, finally sample is subjected to micro-arc oxidation treatment in the electrolyte containing potassium permanganate additive, can prepare that thickness is uniform, hardness is high, the differential arc oxidation film layer with excellent corrosion resistance on aluminum alloy sample surface.This method can not only improve differential arc oxidation film layer performance, but also can effectively promote the growth rate of differential arc oxidation film layer, reduce consumed energy in micro-arc oxidation process, reduce specific energy consumption.In addition, the electrolyte composition that this method uses is simple, it is convenient to prepare, small to human body and environmental hazard.
Description
Technical field
The invention belongs to the field of surface treatment of aluminium alloy, and in particular to a kind of low energy consumption aluminum alloy differential arc oxidation film layer system
Preparation Method.
Background technique
Differential arc oxidization technique is a kind of metal material surface ceramic skill developed on the basis of anodizing technology
Art.One layer, which can be prepared, in aluminum alloy surface using micro-arc oxidation process appropriate has good corrosion resistance and wearability, higher
The ceramic layer of hardness and electrical insulating property.Compared with the film layer of the sufacings such as traditional anodic oxidation, chemical conversion preparation, the differential of the arc
The properties of oxidation film layer significantly improve, and have many advantages, such as simple process, easily operated, in automobile, ship, electricity Gong electricity
The industrial applications such as son, aerospace, machinery have a extensive future.
Although differential arc oxidization technique has many good qualities, but also have the deficiency of its technology itself, and wherein high energy consumption is most heavy
The shortcomings that wanting.Since differential arc oxidization technique is the metal surface treatment technology carried out under high voltage, high current density, unit
Energy consumption is relatively high, improves production cost.And when the technology is applied to the processing of large-area metal material surface, due to height
Energy consumption causes to propose very high requirement to the power and stability of mao power source.Further, since when differential arc oxidation reacts
Part electric energy is converted into thermal energy, releases a large amount of heat, for the stability for guaranteeing micro-arc oxidation process, needs powerful system
Cold heat dissipation equipment, this undoubtedly increases equipment input cost again, and improves production cost.High energy consumption in micro-arc oxidation process
Problem seriously hinders its industrial applications process, thus realizes that the low energy consumption preparation of differential arc oxidation film layer is that the technology is further
Expand the key point of industrial applications.
Currently, people have carried out some research element of arc under low energy consumption oxidation technology on different metal matrix.Harbin
Polytechnical university Wang Xiaobo (Wang Xiaobo low energy consumption magnesium alloy differential arc oxidation electrolyte design and Additive Mechanism Study [D]
Harbin Institute of Technology, 2012.) in the differential arc oxidation research process of magnesium alloy, the ingredient of micro-arc oxidation electrolyte is carried out
Design, develops a kind of Microarc oxidation electrolyte formula of low energy consumption, by introducing NaF, Na in the electrolytic solution2CO3、
(NaPO3)6Additive reduces the specific energy consumption of magnesium alloy differential arc oxidation.But its electrolyte composition is complicated, additive types
It is more, cause electrolyte quota cumbersome, and increase production cost.University On The Mountain Of Swallows Shen De waits so long people (Shen Dejiu, Zou
Jie, Wu Lailei, et al. Effect of high temperature oxidation prefab film on
formation of micro-arc oxidation coatings on 6061aluminum alloy[J]. Applied
Surface Science, 2013,265 (265): 431-437.) by 500 DEG C of high temperature oxidation process 100h, in 6061 aluminium
Alloy surface prepares high-temperature oxydation film layer, studies its influence to micro-arc oxidation process and film layer.The result shows that high temperature oxide film
Arcing voltage can be reduced and shorten arcing time, differential arc oxidation film layer growth course is changed, to improve coating growth
Rate, and improve differential arc oxidation film layer surface topography.But big energy is consumed in 500 DEG C of high-temperature oxydation 100h, and
The thickness uniformity of high temperature oxide film is poor.South China Science & Engineering University Dong Wenxiao (Dong Wenxiao ZL104 chemical conversion-differential arc oxidation
Research [D] the South China Science & Engineering University of combination process, 2015.) by the way that chemical conversion technology is mutually tied with differential arc oxidization technique
It closes, explores the element of arc under low energy consumption oxide production process of ZL104 aluminium alloy, discovery chemical passivation film can weaken ZL104 aluminium alloy
The adverse effect that middle element silicon generates early period in differential arc oxidation, and arcing time can be shortened, it reduces in micro-arc oxidation process
Operating voltage, to reduce the energy consumption of micro-arc oxidation process.But since chemical conversion treatment needs are containing Cr6+Ion it is molten
It is carried out in liquid, Cr VI is a kind of strong carcinogen, seriously endangers natural environment and human health.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of low energy consumption aluminum alloy differential arc oxidation film layer, present invention process
Easy to operate, coating growth rate is fast, and specific energy consumption is low, and electrolyte composition is simple, and environmental pollution is small, prepared differential of the arc oxygen
Changing film layer has excellent corrosion resistance and high rigidity.
A kind of low energy consumption aluminum alloy differential arc oxidation preparation method, includes the following steps:
(1) pre-treatment: carrying out sanding and polishing to aluminum alloy sample, then cleaned, alkaline etching and pickling, then cleaning,
It dries up spare.Specific steps are as follows: by sample respectively on the sand paper of 400#, 800#, 1000#, 1200#, 1500#, 2000# step by step
Then polishing carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder, using dehydrated alcohol and deionized water to polishing after
Sample cleaned.Then, sample 30 ~ 120s of soaking at room temperature in 10g/L sodium hydroxide solution, removal natural oxide film and
Grease is rinsed after immersion with deionized water.Using the mixed solution of sulfuric acid (100-150g/L) and nitric acid (50-100g/L) to sample
Product carry out 60 ~ 180s of soaking at room temperature, removal sample surfaces dust and neutralization residual lye, are rinsed after the completion of processing with deionized water
Sample then dries up spare.
(2) sample Jing Guo pre-treatment anodized: is subjected to anodic oxidation in sulfuric acid and boric acid mixed solution
Processing.The ingredient of anodic oxidation electrolyte is the sulfuric acid of 100 ~ 180g/L and the boric acid of 5 ~ 10g/L.When anodized, with
Sample by pre-treatment is as anode, and stainless steel substrates are as cathode.Technological parameter are as follows: DC constant voltage mode, voltage be 10 ~
20V, processing time are 5 ~ 30min, and electrolyte temperature is 20 ± 1 DEG C, and continues to stir.
(3) electrolytic deposition: using the sample Jing Guo anodized as working electrode, using stainless steel substrates as to electricity
Pole, between two electrodes apply frequency be 50Hz, the alternating current that voltage is 5 ~ 15V, in specific acid metal salting liquid
Electrolytic deposition is carried out, electrolyte temperature is 20 ~ 25 DEG C, and the processing time is 5 ~ 15min, and continues to stir.Alternating current electrolysis deposits institute
With electrolyte by 3 ~ 30g/L of metal salt, 5 ~ 15g/L of sulfuric acid and deionized water composition.Metal salt can for copper sulphate, silver nitrate,
Stannous sulfate, nickel sulfate, any one in cobaltous sulfate.
(4) micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, yin
The area ratio of pole and anode should be not less than 3:1.Micro-arc oxidation electrolyte is by 5 ~ 30g/L of sodium metasilicate, 5 ~ 30g/L of sodium phosphate, hydrogen-oxygen
Change 0.5 ~ 6g/L of sodium, 0.5 ~ 5g/L of potassium permanganate and deionized water composition.Sample is carried out using dipulse mao power source
Micro-arc oxidation treatment, technological parameter are as follows: constant current mode, 5 ~ 12A/dm of current density2, 300 ~ 800Hz of frequency, duty ratio 20% ~
60%, positive negative pulse stuffing ratio (3 ~ 9): 1,15 ~ 20min of time is handled, electrolyte temperature maintains 45 DEG C or less.After treatment, will
Sample taking-up is rinsed with deionized water, is subsequently dried.
After above-mentioned steps are handled, thickness can be obtained uniformly and property with lower specific energy consumption on aluminum alloy sample surface
The excellent differential arc oxidation film layer of energy.
The present invention is suitable for the aluminium alloys such as 1XXX system (fine aluminium), 5XXX system (Al-Mg system), 6XXX system (Al-Mg-Si system),
The aluminium alloy of these series is able to carry out anodized, and has good machine-shaping property and mechanical property,
Industrial circle is widely used.
Processing step, technological parameter and the solution composition that the present invention limits are obtained on the basis of lot of experimental data
's.The anode oxidation membrane for being 5 ~ 28 μm in aluminum alloy sample Surface Creation a layer thickness by anodized, this layer of sun
Pole oxidation film can transform into differential arc oxidation film layer during subsequent micro-arc oxidation treatment, reduce generation micro-arc oxidation films
Energy needed for layer, while this layer of anode oxide film can effectively shorten the time of differential of the arc generation, make differential arc oxidation reaction can
More quickly carry out.The present invention deposits nanometer with good conductivity also by the method for electrolytic deposition in anode oxidation membrane
Metallic particles, effectively reduces the impedance value of anode oxidation membrane, so that reducing the film layer in micro-arc oxidation process punctures institute
The voltage value needed, further decreases the energy consumption in micro-arc oxidation process.In addition, the present invention is micro- in sodium metasilicate-sodium phosphate system
Appropriate potassium permanganate is added in arc oxidation electrolyte, can be substantially reduced the arcing voltage and operating voltage of differential arc oxidation.Moreover,
Potassium permanganate can participate in the oxidation reaction of aluminium substrate, further promote differential arc oxidation film layer as a kind of strong oxidizer
It generates, improves the growth rate of differential arc oxidation film layer, reduce specific energy consumption.
Remarkable advantage of the invention is:
1. differential arc oxidation film layer growth rate of the present invention prepared by aluminum alloy surface is fast, specific energy consumption is low, with tradition
Differential arc oxidization technique compares, and specific energy consumption of the invention is reduced up to 30% or more.
2. differential arc oxidation film layer corrosion resistance of the present invention prepared by aluminum alloy surface is good, hardness is high, closes with aluminium
Gold substrate is firmly combined.
3. present invention process is easy to operate, the electrolyte composition of use is simple, and it is convenient to prepare, and raw material sources are abundant, to people
Body and environmental hazard are small.
Detailed description of the invention
Fig. 1 is the Cross Section Morphology figure of differential arc oxidation sample prepared by different comparative examples and embodiment :(a) comparative example 1；(b)
Embodiment 1；(c) embodiment 2；(d) embodiment 3.
Specific embodiment
Below with reference to comparative example and embodiment, the present invention is further elaborated, but is not limitation of the invention.
The method for measuring thickness of differential arc oxidation film layer is, by observe simultaneously random measurement 30 to example cross section pattern
The thicknesses of layers of a position calculates its average value.The film hardness of sample after differential arc oxidation is measured using micro Vickers.
The corrosion resistance test method of sample is after differential arc oxidation, and sample is carried out polarization curve survey in the NaCl solution of 3.5wt%
Examination, 25 DEG C of solution temperature, sweep speed 5mV/s is available from corrosion electric current density icorrWith polarization resistance Rp, icorrIt is smaller, Rp
It is bigger, illustrate that material corrosion resistance is better.
Formula used in differential arc oxidation energy consumption calculation are as follows:
Wherein, ρ is the energy consumption (kwh/ (m for generating unit volume differential arc oxidation film layer2μm))；I is effective current
(A), value is equal to peak point current I0With the product of duty ratio；S is surface area of sample (cm2)；D is thicknesses of layers (μm).
Comparative example 1
Pre-treatment: 6061 aluminum alloy samples are successively used to the sand of 400#, 800#, 1000#, 1200#, 1500#, 2000#
Paper is polished step by step, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample is surpassed in dehydrated alcohol
Sound cleans 5min, is rinsed after taking-up with deionized water.Then, sample impregnates 80s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Then, sample 130s is impregnated using the mixed solution of 130g/L sulfuric acid and 90g/L nitric acid, taken out
It is rinsed and is dried up spare with deionized water after sample.
Micro-arc oxidation treatment: 6061 aluminum alloy samples Jing Guo pre-treatment are placed in prepared electrolyte, differential of the arc oxygen
Change electrolyte composition is 10g/L sodium metasilicate, 30g/L sodium phosphate, 2g/L sodium hydroxide and deionized water.Using sample as anode,
Using stainless steel substrates as cathode, the area ratio of cathode and anode is 4:1, carries out micro-arc oxidation treatment.Technological parameter are as follows: constant current mould
Formula, current density 10A/dm2, frequency 500Hz, duty ratio 40%, positive negative pulse stuffing ratio 3:1, the processing time is 20min, differential arc oxidation
Using low temperature water-bath control electrolyte temperature at 45 DEG C or less when processing.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.The average thickness of the differential arc oxidation film layer is 17.0 μm, and growth rate is 0.85 μm/min, and specific energy consumption is
3.09kw·h/(m2μm), hardness 1081HV, corrosion current density icorrIt is 7.86 × 10-8A/cm2, polarization resistance Rp
It is 4.85 × 105Ω/cm2。
Embodiment 1
Pre-treatment: 6061 aluminum alloy samples are successively used to the sand of 400#, 800#, 1000#, 1200#, 1500#, 2000#
Paper is polished step by step, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample is surpassed in dehydrated alcohol
Sound cleans 5min, is rinsed after taking-up with deionized water.Then, sample impregnates 120s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Then, sample 100s is impregnated using the mixed solution of 150g/L sulfuric acid and 50g/L nitric acid, taken out
It is rinsed and is dried up spare with deionized water after sample.
Anodized: using 6061 aluminum alloy samples Jing Guo pre-treatment as anode, using stainless steel substrates as cathode,
Anodized is carried out in the mixed solution that concentration is 150g/L sulfuric acid and 10g/L boric acid, applies voltage 15V, when processing
Between be 30min, electrolyte temperature is controlled at 20 ± 1 DEG C using low temperature water-bath in treatment process, and continue to stir.
Electrolytic deposition: using the sample Jing Guo anodized as working electrode, using stainless steel substrates as to electrode,
The 15V alternating current for applying 50Hz between two electrodes, in the electrolyte that 30g/L copper sulphate and 10g/L sulfuric acid form at room temperature into
Row electrolytic deposition 5min, guarantees that solution composition is equal using churned mechanically mode in electrolyting precipitation process by 20 DEG C of electrolyte temperature
It is even.
Micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, cathode and
The area ratio of anode is 4:1.Micro-arc oxidation electrolyte ingredient be 10g/L sodium metasilicate, 30g/L sodium phosphate, 2g/L sodium hydroxide,
2.5g/L potassium permanganate and deionized water.Technological parameter are as follows: constant current mode, current density 10A/dm2, frequency 500Hz, duty ratio
40%, positive negative pulse stuffing ratio 3:1 handle time 20min, using low temperature water-bath control electrolyte temperature 45 when micro-arc oxidation treatment
DEG C or less.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.For the average thickness of differential arc oxidation film layer up to 36.6 μm, growth rate is 1.83 μm/min, and specific energy consumption is
1.49kw·h/(m2μm), hardness 1520HV, corrosion current density icorrIt is 2.50 × 10-9A/cm2, polarization resistance Rp
It is 1.37 × 107Ω/cm2。
Embodiment 2
Pre-treatment: 6061 aluminum alloy samples are successively used to the sand of 400#, 800#, 1000#, 1200#, 1500#, 2000#
Paper is polished step by step, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample is surpassed in dehydrated alcohol
Sound cleans 5min, is rinsed after taking-up with deionized water.Then, sample impregnates 60s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Then, sample 60s is impregnated using the mixed solution of 100g/L sulfuric acid and 100g/L nitric acid, taken out
It is rinsed and is dried up spare with deionized water after sample.
Anodized: using 6061 aluminum alloy samples Jing Guo pre-treatment as anode, using stainless steel substrates as cathode,
Anodized is carried out in the mixed solution that concentration is 135g/L sulfuric acid and 8g/L boric acid, applies voltage 10V, handles the time
For 5min, electrolyte temperature is controlled at 20 ± 1 DEG C using low temperature water-bath in treatment process.
Electrolytic deposition: using the sample Jing Guo anodized as working electrode, using stainless steel substrates as to electrode,
The 5V alternating current for applying 50Hz between two electrodes carries out at room temperature in the electrolyte that 3g/L silver nitrate and 15g/L sulfuric acid form
Electrolytic deposition 15min, guarantees that solution composition is equal using churned mechanically mode in electrolyting precipitation process by 22 DEG C of electrolyte temperature
It is even.
Micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, cathode and
The area ratio of anode is 6:1.Micro-arc oxidation electrolyte ingredient be 30g/L sodium metasilicate, 18g/L sodium phosphate, 6g/L sodium hydroxide,
2g/L potassium permanganate and deionized water.Technological parameter are as follows: constant current mode, current density 5A/dm2, frequency 800Hz, duty ratio
60%, positive negative pulse stuffing ratio 3:1 handle time 20min, using low temperature water-bath control electrolyte temperature 45 when micro-arc oxidation treatment
DEG C or less.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.For the average thickness of differential arc oxidation film layer up to 29.6 μm, growth rate is 1.48 μm/min, and specific energy consumption is
1.79kw·h/(m2μm), hardness 1252HV, corrosion current density icorrIt is 4.57 × 10-9A/cm2, polarization resistance Rp
It is 8.79 × 106Ω/cm2。
Embodiment 3
Pre-treatment: 6061 aluminum alloy samples are successively used to the sand of 400#, 800#, 1000#, 1200#, 1500#, 2000#
Paper is polished step by step, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample is surpassed in dehydrated alcohol
Sound cleans 5min, is rinsed after taking-up with deionized water.Then, sample impregnates 30s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Then, sample 180s is impregnated using the mixed solution of 150g/L sulfuric acid and 60g/L nitric acid, taken out
It is rinsed and is dried up spare with deionized water after sample.
Anodized: using 6061 aluminum alloy samples Jing Guo pre-treatment as anode, using stainless steel substrates as cathode,
Anodized is carried out in the mixed solution that concentration is 100g/L sulfuric acid and 5g/L boric acid, applies voltage 20V, handles the time
For 18min, electrolyte temperature is controlled at 20 ± 1 DEG C using low temperature water-bath in treatment process.
Electrolytic deposition: using the sample Jing Guo anodized as working electrode, using stainless steel substrates as to electrode,
The 15V alternating current for applying 50Hz between two electrodes, in the electrolyte that 12g/L nickel nitrate and 10g/L sulfuric acid form at room temperature into
Row electrolytic deposition 10min, guarantees that solution composition is equal using churned mechanically mode in electrolyting precipitation process by 25 DEG C of electrolyte temperature
It is even.
Micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, cathode and
The area ratio of anode is 10:1.Micro-arc oxidation electrolyte ingredient be 5g/L sodium metasilicate, 20g/L sodium phosphate, 0.5g/L sodium hydroxide,
5g/L potassium permanganate and deionized water.Technological parameter are as follows: constant current mode, current density 12A/dm2, frequency 300Hz, duty ratio
50%, positive negative pulse stuffing ratio 9:1 handle time 20min, using low temperature water-bath control electrolyte temperature 45 when micro-arc oxidation treatment
DEG C or less.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.For the average thickness of differential arc oxidation film layer up to 34.8 μm, growth rate is 1.74 μm/min, and specific energy consumption is
1.65kw·h/(m2μm), hardness 1400HV, corrosion current density icorrIt is 4.26 × 10-9A/cm2, polarization resistance Rp
It is 9.61 × 106Ω/cm2。
Comparative example 2
Pre-treatment: by 1060 aluminium alloys successively use the sand paper of 400#, 800#, 1000#, 1200#, 1500#, 2000# by
Grade polishing, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample carries out ultrasonic clear in dehydrated alcohol
5min is washed, is rinsed after taking-up with deionized water.Then, sample impregnates sample 50s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Sample 100s is impregnated using the nitric acid solution of 100g/L sulfuric acid and 50g/L, is spent after taking out sample
Ionized water is rinsed and is dried up spare.
Micro-arc oxidation treatment: 1060 aluminum alloy samples through pre-treatment are placed in prepared electrolyte, differential arc oxidation
Electrolyte composition is 25g/L sodium metasilicate, 5g/L sodium phosphate, 4g/L sodium hydroxide and deionized water.Using sample as anode, with not
The steel disc that becomes rusty is used as cathode, and the area ratio of cathode and anode is 8:1.Carry out micro-arc oxidation treatment.Technological parameter are as follows: constant current mode,
Current density 5A/dm2, duty ratio 20%, positive negative pulse stuffing ratio 8:1, frequency 400Hz handle time 18min, when micro-arc oxidation treatment
Using low temperature water-bath control electrolyte temperature at 45 DEG C or less.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.The average thickness of the differential arc oxidation film layer is 13.7 μm, and growth rate is 0.76 μm/min, and specific energy consumption is
3.34kw·h/(m2μm), hardness 1295HV, corrosion current density icorrIt is 2.87 × 10-8A/cm2, polarization resistance Rp
It is 8.40 × 105Ω/cm2。
Embodiment 4
Pre-treatment: by 1060 aluminium alloys successively use the sand paper of 400#, 800#, 1000#, 1200#, 1500#, 2000# by
Grade polishing, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample carries out ultrasonic clear in dehydrated alcohol
5min is washed, is rinsed after taking-up with deionized water.Then, sample impregnates sample 50s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Sample 70s is impregnated using the nitric acid solution of 120g/L sulfuric acid and 60g/L, is spent after taking out sample
Ionized water is rinsed and is dried up spare.
Anodized: using 1060 aluminum alloy samples Jing Guo pre-treatment as anode, using stainless steel substrates as cathode,
Anodized is carried out in the mixed solution that concentration is 180g/L sulfuric acid and 5g/L boric acid, applies voltage 15V, handles the time
For 20min, electrolyte temperature is controlled at 20 DEG C ± 1 DEG C or so using low temperature water-bath in treatment process.
Electrolytic deposition: being to electrode, two with stainless steel substrates using the sample Jing Guo anodized as working electrode
Apply the 15V alternating current of 50Hz between electrode, electrolyte composition is in the electrolyte that 15g/L cobaltous sulfate and 12g/L sulfuric acid form
Electrolytic deposition 8min is carried out at room temperature, 22 DEG C of electrolyte temperature, uses churned mechanically mode to guarantee in electrolyting precipitation process molten
Liquid ingredient is uniform.
Micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, cathode and
The area ratio of anode is 8:1.Micro-arc oxidation electrolyte ingredient be 25g/L sodium metasilicate, 5g/L sodium phosphate, 4g/L sodium hydroxide,
0.5g/L potassium permanganate and deionized water.Technological parameter are as follows: constant current mode, current density 5A/dm2, frequency 400Hz, duty ratio
20%, positive negative pulse stuffing ratio 8:1 handle time 18min, using low temperature water-bath control electrolyte temperature 45 when micro-arc oxidation treatment
DEG C or less.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.For the average thickness of differential arc oxidation film layer up to 25.3 μm, growth rate is 1.41 μm/min, and specific energy consumption is
1.76kw·h/(m2μm), hardness 1470HV, corrosion current density icorrIt is 5.05 × 10-9A/cm2, polarization resistance Rp
It is 6.96 × 106Ω/cm2。
Comparative example 3
Pre-treatment: by 5052 aluminium alloys successively use the sand paper of 400#, 800#, 1000#, 1200#, 1500#, 2000# by
Grade polishing, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample carries out ultrasonic clear in dehydrated alcohol
5min is washed, is rinsed after taking-up with deionized water.Then, sample impregnates sample 40s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Sample 120s is impregnated using the nitric acid solution of 100g/L sulfuric acid and 80g/L, is spent after taking out sample
Ionized water is rinsed and is dried up spare.
Micro-arc oxidation treatment: 5052 aluminum alloy samples through pre-treatment are placed in prepared electrolyte, differential arc oxidation
Electrolyte composition is 25g/L sodium metasilicate, 25g/L sodium phosphate, 1.5g/L sodium hydroxide and deionized water.Using sample as anode,
Using stainless steel substrates as cathode, the area ratio of cathode and anode is 12:1, carries out micro-arc oxidation treatment.Technological parameter are as follows: constant current
Mode, current density 12A/dm2, duty ratio 60%, frequency 700Hz, positive negative pulse stuffing ratio 9:1 handle time 15min, differential arc oxidation
Using low temperature water-bath control electrolyte temperature at 45 DEG C or less when processing.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.The average thickness of the differential arc oxidation film layer is 14.3 μm, and growth rate is 0.95 μm/min, and specific energy consumption is
3.45kw·h/(m2μm), hardness 1316HV, corrosion current density icorrIt is 6.6 × 10-8A/cm2, polarization resistance RpFor
5.34×105Ω/cm2。
Embodiment 5
Pre-treatment: by 5052 aluminium alloys successively use the sand paper of 400#, 800#, 1000#, 1200#, 1500#, 2000# by
Grade polishing, carries out mechanical polishing processing using 0.5 μm of aluminum oxide polishing powder.Then, sample carries out ultrasonic clear in dehydrated alcohol
5min is washed, is rinsed after taking-up with deionized water.Then, sample impregnates sample 40s in 10g/L sodium hydroxide solution, takes out sample
It is rinsed after product with deionized water.Sample 110s is impregnated using the nitric acid solution of 120g/L sulfuric acid and 80g/L, is spent after taking out sample
Ionized water is rinsed and is dried up spare.
Anodized: using 5052 aluminum alloy samples Jing Guo pre-treatment as anode, using stainless steel substrates as cathode,
Anodized is carried out in the mixed solution that concentration is 160g/L sulfuric acid and 7g/L boric acid, applies voltage 20V, handles the time
For 12min, electrolyte temperature is controlled at 20 DEG C ± 1 DEG C or so using low temperature water-bath in treatment process.
Electrolytic deposition: using the sample Jing Guo anodized as working electrode, using stainless steel substrates as to electrode,
The 12V alternating current for applying 50Hz between two electrodes, in the electrolyte that 25g/L stannous sulfate and 10g/L sulfuric acid form at room temperature
Electrolytic deposition 10min is carried out, 23 DEG C of electrolyte temperature, solution composition is guaranteed using churned mechanically mode in electrolyting precipitation process
Uniformly.
Micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, cathode and
The area ratio of anode is 12:1.Micro-arc oxidation electrolyte ingredient is 25g/L sodium metasilicate, 25g/L sodium phosphate, 1.5g/L hydroxide
Sodium, 1.8g/L potassium permanganate and deionized water.Technological parameter are as follows: constant current mode, current density 12A/dm2, duty ratio 60%, frequency
Rate 700Hz, positive negative pulse stuffing ratio 9:1 handle time 15min, control electrolyte temperature using low temperature water-bath when micro-arc oxidation treatment
At 45 DEG C or less.
Finally, the sample after micro-arc oxidation treatment is taken out, rinsed well with deionized water, phase is carried out to sample after drying
Close measurement.For the average thickness of differential arc oxidation film layer up to 28.2 μm, growth rate is 1.88 μm/min, and specific energy consumption is
1.54kw·h/(m2μm), hardness 1506HV, corrosion current density icorrIt is 5.30 × 10-9A/cm2, polarization resistance Rp
It is 4.46 × 106Ω/cm2。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of low energy consumption aluminum alloy differential arc oxidation film layer preparation method, which comprises the steps of:
(1) pre-treatment: carrying out sanding and polishing to aluminum alloy sample, then cleaned, alkaline etching and pickling, then cleans, dries up
It is spare；
(2) sample Jing Guo pre-treatment anodized: is subjected to anodized in sulfuric acid and boric acid mixed solution；
When anodized, using the sample Jing Guo pre-treatment as anode, stainless steel substrates are as cathode, technological parameter are as follows: direct current is permanent
Die pressing type, voltage are 10 ~ 20V, and the processing time is 5 ~ 30min, and electrolyte temperature is 20 ± 1 DEG C, and continues to stir；
(3) electrolytic deposition: using the sample Jing Guo anodized as working electrode, using stainless steel substrates as to electrode,
Apply between two electrodes frequency be 50Hz, the alternating current that voltage is 5 ~ 15V, it is heavy that electrolysis is carried out in acid metal salting liquid
Product, electrolyte temperature are 20 ~ 25 DEG C, and the processing time is 5 ~ 15min, and continues to stir；
(4) micro-arc oxidation treatment: using the sample after electrolytic deposition as anode, using stainless steel substrates as cathode, cathode and
The area ratio of anode should be not less than 3:1；Micro-arc oxidation electrolyte is by 5 ~ 30g/L of sodium metasilicate, 5 ~ 30g/L of sodium phosphate, sodium hydroxide
0.5 ~ 6g/L, 0.5 ~ 5g/L of potassium permanganate and deionized water composition carry out the differential of the arc to sample using dipulse mao power source
Oxidation processes, technological parameter are as follows: constant current mode, 5 ~ 12A/dm of current density2, 300 ~ 800Hz of frequency, duty ratio 20% ~ 60%, just
Negative pulse ratio (3 ~ 9): 1,15 ~ 20min of time is handled, electrolyte temperature is lower than 45 DEG C, and after treatment spends sample taking-up
Ionized water rinses, and is subsequently dried；
After above-mentioned steps are handled, differential arc oxidation film layer is obtained on aluminum alloy sample surface.
2. preparation method according to claim 1, which is characterized in that step (1) is described, the pretreatment process of sample are as follows:
Sample is polished on the sand paper of 400#, 800#, 1000#, 1200#, 1500#, 2000# step by step respectively, then uses 0.5 μm of oxygen
Change aluminium polishing powder and carry out mechanical polishing processing, the sample after polishing is cleaned using dehydrated alcohol and deionized water；Then,
Sample 30 ~ 120s of soaking at room temperature in 10g/L sodium hydroxide solution removes natural oxide film and grease, uses deionization after immersion
Water rinses；60 ~ 180s of soaking at room temperature is carried out to sample using the mixed solution of sulfuric acid and nitric acid, removal sample surfaces dust is in
With residual lye, deionized water lavage specimens product are used after the completion of processing, are then dried up spare.
3. preparation method according to claim 1, which is characterized in that step (2) is described, the composition of anodic oxidation electrolyte
For the sulfuric acid of 100 ~ 180g/L and the boric acid of 5 ~ 10g/L.
4. preparation method according to claim 1, which is characterized in that step (3) is described, and alternating current electrolysis deposition is used acid
Metal salt solution is copper sulphate, silver nitrate, sulphur by 3 ~ 30g/L of metal salt, 5 ~ 15g/L of sulfuric acid and deionized water composition, metal salt
Sour stannous, nickel sulfate, any one in cobaltous sulfate.
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| CN103726093A (en) * | 2013-12-04 | 2014-04-16 | 武汉材料保护研究所 | Method of adopting environment-friendly nickel-containing electrolyte to prepare microarc oxidation film layer on surface of magnesium alloy |
| CN105018999A (en) * | 2015-07-09 | 2015-11-04 | 哈尔滨工程大学 | Method for growing layered doubled hydroxide on aluminum alloy micro-arc oxidation film in situ |
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| CN101845652A (en) * | 2010-03-17 | 2010-09-29 | 中国船舶重工集团公司第十二研究所 | Method for preparing micro-arc oxide film layer |
| CN103726093A (en) * | 2013-12-04 | 2014-04-16 | 武汉材料保护研究所 | Method of adopting environment-friendly nickel-containing electrolyte to prepare microarc oxidation film layer on surface of magnesium alloy |
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