CN108728883A - Floride-free micro-arc oxidation electrolyte, differential arc oxidation method and products thereof - Google Patents
Floride-free micro-arc oxidation electrolyte, differential arc oxidation method and products thereof Download PDFInfo
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- CN108728883A CN108728883A CN201710262189.5A CN201710262189A CN108728883A CN 108728883 A CN108728883 A CN 108728883A CN 201710262189 A CN201710262189 A CN 201710262189A CN 108728883 A CN108728883 A CN 108728883A
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- arc oxidation
- floride
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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Abstract
The invention belongs to field of metal surface treatment technology, it is specifically related to a kind of floride-free micro-arc oxidation electrolyte, differential arc oxidation method and products thereof, for carrying out differential arc oxidation processing to Mg alloy surface.Floride-free micro-arc oxidation electrolyte, with densimeter, including:Film forming agent 5g/L-20g/L, acid-base modifier 4g/L-20g/L, no fluoride mixture 5g/L-8g/L, solvent is water.Differential arc oxidation method includes:First, pre-treatment is carried out to alloy workpiece surface;Then, floride-free micro-arc oxidation electrolyte is added in a cell;Thereafter, electrical parameter is set, is powered on, differential arc oxidation is carried out to alloy workpiece;Then, it is cleaned and is toasted;Finally carry out correlated performance test.The magnesium-alloy material film adhesion obtained in aforementioned manners is good and excellent corrosion resistance.Material source used in the present invention is extensive, of low cost and free from environmental pollution, is suitable for mass production correlation magnesium-alloy material.
Description
【Technical field】
The invention belongs to field of metal surface treatment technology, it is specifically related to a kind of floride-free micro-arc oxidation electrolyte, the differential of the arc
Method for oxidation and products thereof.
【Background technology】
Differential arc oxidization technique refers to being enhanced using arc discharge and being activated in anode on the basis of common anode aoxidizes
The reaction of upper generation, to form good reinforcing ceramic membrane by the workpiece surface of material of aluminium, titanium, magnesium metal and its alloy
Method.By applying voltage on workpiece with dedicated mao power source, make the metal and electrolyte solution of workpiece surface
Interaction forms micro-arc discharge in workpiece surface, and under the action of the factors such as high temperature, electric field, metal surface forms ceramic membrane,
Achieve the purpose that workpiece surface is strengthened.
At this stage, most of electrolyte of differential arc oxidization technique generally use is with silicate, phosphate-based, aluminate-series
Based on.Fluoride is usually contained in the film forming agent added so that entire micro-arc oxidation process has the participation of fluoride.In this way
Primarily to film forming is easy, and obtained ceramic membrane corrosion resistance is preferable after adding fluoride.But fluoride meeting
Environment is polluted, if human body takes in more fluorine, is easy to suffer from fluorosis of bone.
In view of this, it is really necessary to develop a kind of floride-free micro-arc oxidation electrolyte, to solve the above problems.
【Invention content】
Therefore, the purpose of the present invention is to provide a kind of floride-free micro-arc oxidation electrolytes, and micro- using the progress of this electrolyte
The method of arc oxidation and acquired magnesium-alloy material.The free-floride micro-arc oxidation electrolyte not fluoride, therefore will not be to environment
It pollutes.Carrying out differential arc oxidation equally using such electrolyte can realize that film forming is easy, corrosion resistant purpose after film forming.
In order to achieve the above object, with densimeter, which includes:
Film forming agent, 5g/L-20g/L;
Acid-base modifier, 4g/L-20g/L;
Without fluoride mixture, 5g/L-8g/L;
Solvent is water.
Optionally, the film forming agent is silicate, and phosphate is one or more in aluminate.
Optionally, the acid-base modifier is one kind in sodium hydroxide or potassium hydroxide.
Optionally, the no fluoride mixture is trisodium citrate, molybdate, tungstates, carbonate, aluminate, six inclined phosphorus
It is one or more in hydrochlorate, titanium potassium oxalate, tartaric acid, sodium phosphate, Boratex, calcium carbonate, titanium dioxide, phytate.
It is as follows with the simplified process that this free-floride micro-arc oxidation electrolyte handles alloy surface:First, pairing metal working
Part surface carries out pre-treatment;Then, floride-free micro-arc oxidation electrolyte is added in a cell;Thereafter, power on, set electricity
Parameter carries out differential arc oxidation to magnesium alloy workpiece;Finally, it is cleaned and is toasted.
Then, the magnesium alloy workpiece after differential arc oxidation is tested for the property.It is tested by coating mesh segmentation, glue of tearing
After band, lose paint particle on adhesive tape;It tests, is found without peeling paint, also without substrate loss by scratch resistance performance;By salt fog
After test, Mg alloy surface is corrosion-free without fading.
Compared to the prior art, floride-free micro-arc oxidation electrolyte of the invention will not produce health and ecological environment
Raw harmful effect.Also, using the electrolyte to alloy carry out differential arc oxidation processing, obtained product film adhesion it is good and
Excellent corrosion resistance.Material source used in the present invention is extensive, of low cost and free from environmental pollution, is suitable for mass production
Related magnesium-alloy material.
【Description of the drawings】
Fig. 1 is painted the flow diagram of differential arc oxidation.
Fig. 2 is painted magnesium alloy trial-production piece and carries out the schematic diagram after salt spray test.
【Specific implementation mode】
To have further understanding to the purpose of the present invention, method and step and effect, floride-free differential arc oxidation is electrolysed below
The preparation of liquid carries out the processing procedure of differential arc oxidation to Mg alloy surface using above-mentioned floride-free micro-arc oxidation electrolyte and obtains
The correlated performance test of product is described in detail respectively.
It is the configuration process of floride-free micro-arc oxidation electrolyte first.Using deionized water as solvent, in 15-60 DEG C of temperature
Under, sequentially add following components:It is added without fluoride mixture 5g/L-8g/L, stirring is until be completely dissolved;It is added 5g/L-20g/L's
Film forming agent is uniformly mixed;The acid-base modifier of 4g/L-20g/L is added, adjusts the pH value of electrolyte in the range of 8-13;It is quiet
It sets 30 minutes, filters out impurity.
As long as it should be noted that the above components within the scope of respective value, are electrolysed with the floride-free differential arc oxidation that this is prepared
Liquid can be used as the tank liquor of differential arc oxidation.
Optionally, fluorine-free compounds be trisodium citrate, molybdate, tungstates, carbonate, aluminate, hexametaphosphate,
It is one or more in titanium potassium oxalate, tartaric acid, sodium phosphate, Boratex, calcium carbonate, titanium dioxide, phytate.
Optionally, the film forming agent is silicate, and phosphate is one or more in aluminate.
Optionally, acid-base modifier is one kind in sodium hydroxide or potassium hydroxide.
As it can be seen that fluoride is not contained in above-mentioned formula, it is more friendly to environment and human body.
The process that differential arc oxidation is carried out using above-mentioned floride-free micro-arc oxidation electrolyte as tank liquor is as follows:
S101:Piece is manufactured experimently with sand paper polishing magnesium alloy, the greasy dirt on its surface is removed, washes, be dried for standby;
S102:Magnesium alloy trial-production piece is immersed in the floride-free micro-arc oxidation electrolyte, startup power supply equipment carries out
Differential arc oxidation, oxidization time are 3-8 minutes;
S103:The magnesium alloy trial-production piece is taken out, it is cleaned with pure water;
S104:Under conditions of 100-200 DEG C, magnesium alloy trial-production piece is toasted;
S105:Magnesium alloy trial-production piece is tested for the property.
Optionally, step (2) uses current constant control, current density 0.3A/dm2-5A/dm2, ceiling voltage 320V-
450V, duty ratio 10%-35%, frequency 500Hz-1000Hz, positive and negative frequency ratio are 1:1-1:5.
Optionally, in step (2) temperature of floride-free micro-arc oxidation electrolyte by a set of tank liquor temperature control heated and cooled down
System controls and the control of its temperature is near 18 DEG C.
Optionally, the performance test in step (5) is the test of coating mesh segmentation, scratch resistance performance test, salt fog survey respectively
Examination.
Above-mentioned magnesium alloy trial-production piece material therefor is AZ91D magnesium alloys.
Power-supply device used is bidirectional pulse mao power source in above-mentioned processing procedure, and maximum forward current value 30A is born
To electric current 20A, Maximum Forward Voltage 700V, negative voltage 200V.
The electric current of step (2) is set as two benches.One corresponding current density 1 of stage, ceiling voltage 1, oxidization time 1, rank
Two corresponding current density 2 of section, ceiling voltage 2, oxidization time 2.Oxidation process voltage early period is reached in ascending curve trend is stablized
Start steady micro-arc discharge after certain voltage.
In the following, providing 3 embodiments according to different electrical parameters.
Embodiment 1:
Duty ratio:15%;
Frequency:650Hz;
Positive and negative frequency ratio:1:2;
Stage one, current density 1:0.5A/dm2, ceiling voltage 1:330V, oxidization time 1:120s;
Stage two, current density 2:0.3A/dm2, ceiling voltage 2:420V, oxidization time 1:210s.
It is 2.5um to reach thicknesses of layers.
Embodiment 2:
Duty ratio:15%;
Frequency:650Hz;
Positive and negative frequency ratio:1:2;
Stage one, current density 1:0.6A/dm2, ceiling voltage 1:270V, oxidization time 1:80s;
Stage two, current density 2:0.5A/dm2, ceiling voltage 2:340V, oxidization time 1:210s.
It is 3um to reach thicknesses of layers.
Embodiment 3:
Duty ratio:15%;
Frequency:650Hz;
Positive and negative frequency ratio:1:2;
Stage one, current density 1:0.9A/dm2, ceiling voltage 1:300V, oxidization time 1:120s;
Stage two, current density 2:0.7A/dm2, ceiling voltage 2:370V, oxidization time 1:180s.
It is 5um to reach thicknesses of layers.
As seen from the above embodiment, as oxidization time is longer and current density increases, Micro-Arc Oxidized Ceramic Coating
Thickness tends to linearly increase.Therefore, it is not limited only to above-described embodiment, by the way that different electrical parameters is arranged, can be reached not
Same thicknesses of layers.
Piece is manufactured experimently according to the magnesium alloy of the about 5um-8um of the thicknesses of layers to obtaining by the above process to test.Test
As a result following table is please referred to.
Wherein, salt spray test result carries out the signal after salt spray test referring to FIG. 2, Fig. 2 depicts magnesium alloy trial-production piece
Figure.As it can be seen that magnesium alloy trial-production piece surface is corrosion-free without fading.
It should be pointed out that the present invention is not limited to the above embodiment, any person skilled in the art is based on this
Inventive technique scheme both falls within the protection of the present invention to any simple modification, equivalent change and modification made by above-described embodiment
In range.
Claims (10)
1. a kind of free-floride micro-arc oxidation electrolyte, which is characterized in that with densimeter comprising:
Film forming agent, 5g/L-20g/L;
Acid-base modifier, 4g/L-20g/L;
Without fluoride mixture, 5g/L-8g/L;
Solvent is water.
2. free-floride micro-arc oxidation electrolyte according to claim 1, which is characterized in that the film forming agent is silicate, phosphorus
Hydrochlorate, it is one or more in aluminate.
3. free-floride micro-arc oxidation electrolyte according to claim 1, which is characterized in that the acid-base modifier is hydroxide
One kind in sodium or potassium hydroxide.
4. free-floride micro-arc oxidation electrolyte according to claim 1, which is characterized in that the no fluoride mixture is citric acid
Trisodium, molybdate, tungstates, carbonate, aluminate, hexametaphosphate, titanium potassium oxalate, tartaric acid, sodium phosphate, Boratex, carbon
It is one or more in sour calcium, titanium dioxide, phytate.
5. free-floride micro-arc oxidation electrolyte according to claim 1, which is characterized in that the free-floride micro-arc oxidation electrolyte
PH value control in the range of 8.0-13.0.
6. a kind of side carrying out differential arc oxidation using the floride-free micro-arc oxidation electrolyte as described in any one of claim 1 to 5
Method, which is characterized in that including steps are as follows:
(1) piece is manufactured experimently with sand paper polishing magnesium alloy, removes the greasy dirt on its surface, washes, be dried for standby;
(2) magnesium alloy trial-production piece is immersed in the floride-free micro-arc oxidation electrolyte, startup power supply equipment carries out differential of the arc oxygen
Change, oxidization time is 3-8 minutes;
(3) it takes out the magnesium alloy and manufactures experimently piece, it is cleaned with pure water;
(4) under conditions of 100-200 DEG C, magnesium alloy trial-production piece is toasted;
(5) magnesium alloy trial-production piece is tested for the property.
7. differential arc oxidation method according to claim 6, which is characterized in that the step (2) uses current constant control, electric current
Density is 0.3A/dm2-5A/dm2, ceiling voltage 320V-450V, duty ratio 10%-35%, frequency 500Hz-
1000Hz, positive and negative frequency ratio 1:1-1:5.
8. differential arc oxidation method according to claim 6, which is characterized in that floride-free differential arc oxidation electricity in the step (2)
The temperature for solving liquid is controlled by a set of tank liquor temperature control system control heated and cooled down and its temperature near 18 DEG C.
9. differential arc oxidation method according to claim 6, which is characterized in that the performance test difference in the step (5)
It is the test of coating mesh segmentation, scratch resistance performance test, salt spray test.
10. a kind of magnesium-alloy material, which is characterized in that the product is any one of claim 1 to 5 floride-free differential of the arc oxygen
Change the magnesium-alloy material that electrolyte is handled.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114540918A (en) * | 2022-03-25 | 2022-05-27 | 陕西工业职业技术学院 | Electrolyte, preparation method thereof and preparation method of magnesium alloy micro-arc oxidation coating |
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CN1796614A (en) * | 2004-12-20 | 2006-07-05 | 中国科学院金属研究所 | Element of arc oxidation electrolyte of environmental protection type magnesium alloy, and method of element of arc oxidation |
CN103173838A (en) * | 2013-04-11 | 2013-06-26 | 江西科技师范大学 | Magnesium alloy micro-arc oxidation electrolyte and micro-arc oxidation method |
CN105040063A (en) * | 2015-08-21 | 2015-11-11 | 北京石油化工学院 | Preparation method of micro-arc oxidation electrolyte |
CN105603488A (en) * | 2016-03-25 | 2016-05-25 | 北京石油化工学院 | Micro-arc oxidation electrolyte and method for preparing colored ceramic layers on matrix surface |
CN105734639A (en) * | 2016-03-25 | 2016-07-06 | 北京石油化工学院 | Micro-arc oxidation electrolyte and method for preparing golden yellow ceramic layer on surface of matrix |
CN106086993A (en) * | 2016-07-22 | 2016-11-09 | 中国科学院深圳先进技术研究院 | A kind of magnesium alloy differential arc oxidation electrolyte and magnesium alloy differential arc oxidation method |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1796614A (en) * | 2004-12-20 | 2006-07-05 | 中国科学院金属研究所 | Element of arc oxidation electrolyte of environmental protection type magnesium alloy, and method of element of arc oxidation |
CN103173838A (en) * | 2013-04-11 | 2013-06-26 | 江西科技师范大学 | Magnesium alloy micro-arc oxidation electrolyte and micro-arc oxidation method |
CN105040063A (en) * | 2015-08-21 | 2015-11-11 | 北京石油化工学院 | Preparation method of micro-arc oxidation electrolyte |
CN105603488A (en) * | 2016-03-25 | 2016-05-25 | 北京石油化工学院 | Micro-arc oxidation electrolyte and method for preparing colored ceramic layers on matrix surface |
CN105734639A (en) * | 2016-03-25 | 2016-07-06 | 北京石油化工学院 | Micro-arc oxidation electrolyte and method for preparing golden yellow ceramic layer on surface of matrix |
CN106086993A (en) * | 2016-07-22 | 2016-11-09 | 中国科学院深圳先进技术研究院 | A kind of magnesium alloy differential arc oxidation electrolyte and magnesium alloy differential arc oxidation method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114540918A (en) * | 2022-03-25 | 2022-05-27 | 陕西工业职业技术学院 | Electrolyte, preparation method thereof and preparation method of magnesium alloy micro-arc oxidation coating |
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Effective date of registration: 20190830 Address after: 243000 No. 1430 Huxi Southwest Road, Ma'anshan Economic and Technological Development Zone, Anhui Province Applicant after: Huafu Precision Technology (Ma'anshan) Co., Ltd. Address before: Suzhou City, Jiangsu province 215300 Eagle Kunshan Road Development Zone No. 66 Applicant before: Kunshan Han Ding Feinmetall GmbH |
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