CN101928976B - Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof - Google Patents
Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof Download PDFInfo
- Publication number
- CN101928976B CN101928976B CN2010102577496A CN201010257749A CN101928976B CN 101928976 B CN101928976 B CN 101928976B CN 2010102577496 A CN2010102577496 A CN 2010102577496A CN 201010257749 A CN201010257749 A CN 201010257749A CN 101928976 B CN101928976 B CN 101928976B
- Authority
- CN
- China
- Prior art keywords
- exchange membrane
- oxidation
- compartment
- ion
- electrolyte solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to an ion exchange membrane electrolytic bath for the anodic oxidation of a magnetism alloy and an oxidation method thereof, which belong to the technical field of metal surface treatment. The electrolytic bath comprises a cathode chamber and an anode chamber in the cathode chamber, wherein electrolyte solution is filled between the anode chamber and the cathode chamber; both the cathode chamber and the anode chamber have rectangular structures; four side walls of the anode chamber are provided with ion exchange membranes serving as diaphragm walls; and the ion exchange membranes comprise two opposite anion exchange membranes and two opposite cation exchange membranes. The ion exchange membrane electrolytic bath of the invention is suitable for surface anodic (micro-arc or plasma electrolyte) oxidation processes of all magnetism alloys.
Description
Technical field
What the present invention relates to is a kind of device and method of field of metal surface treatment technology, specifically is a kind of ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and method for oxidation thereof.
Background technology
Electric current that anode oxidation process is used or voltage can adopt direct current (D.C.), exchange (A.C.); Perhaps stack of AC and DC (A.C+D.C.) and pulsed current (P.C.).When the curtage that is applied reaches certain value; On oxidized magnesium alloy workpiece, will produce spark (" spark ") or little electric arc (" micro arc "); At this moment; People are called differential arc oxidation (MAO, micro arc oxidation) or microplasma electrolytic solution oxidation (PEO, plasma electrolyte oxidation) with anodic oxidation (anodizing) again.
Existing magnesium alloy anode (differential of the arc or plasma electrolysis liquid) oxidizing process method; Normally will make the anodic magnesium alloy workpiece and be placed on simultaneously with the counter electrode of making negative electrode and be equipped with in the electrolyzer of oxidation with electrolyte solution, promptly anode and negative electrode with contact with a kind of electrolyte solution and do not separate.The electrolyte solution that magnesium alloy anode (differential of the arc or plasma electrolysis liquid) oxidizing process can be selected for use is varied; For example; The aqueous solution that contains chromic salt, phosphoric acid salt, aluminate, silicate, villiaumite, borate or the like, yet, when the magnesiumalloy oxidation contains silicate, aluminate and villiaumite simultaneously with electrolyte solution; Must strictly monitor the pH value of solution at any time, make pH >=11.
Retrieval through to prior art is found, U.S. Patent number US5, and 240,589 have put down in writing its pH value that contains the electrolyte solution of silicate and villiaumite is at least 12.5, i.e. pH >=12.5; U.S. Patent number US5, the pH value of having put down in writing the electrolyte solution that contains silicate and villiaumite in 264,113 is at least 11, i.e. pH >=11;
U.S. Patent number US6,495, the pH value of having put down in writing the electrolyte solution that contains silicate and villiaumite during the summary of the invention of 267B1 is described is at least 11, i.e. pH >=11.Otherwise electrolyte solution will produce silicofluoride and fluoaluminate deposition gradually, thereby causes the electrolyte solution instability until inefficacy.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and method for oxidation thereof are provided; Solve when the magnesiumalloy oxidation contains silicate, aluminate and villiaumite simultaneously with electrolyte solution; Electrolyte solution can produce silicofluoride and fluoaluminate deposition gradually, thereby causes the electrolyte solution instability until the problem that lost efficacy.
The present invention realizes through following technical scheme:
The present invention relates to a kind of ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy, comprising: the anolyte compartment that cathode compartment is inner with placing cathode compartment, wherein: be provided with electrolyte solution between anolyte compartment and the cathode compartment, described cathode compartment and anolyte compartment are rectangular configuration.
Four sidewalls of described anolyte compartment are provided with ion-exchange membrane as partition wall, and this ion-exchange membrane comprises: anion-exchange membrane that is oppositely arranged in twos and cationic exchange membrane.
Be provided with electrolyte solution in the described anolyte compartment, the component of this electrolyte solution and content are: the Pottasium Hydroxide of 5～25g/L or sodium hydroxide; The water glass of 2～25g/L; The sodium metaaluminate of 5～20g/L; The potassium pyrophosphate of 2～10g/L or trisodium phosphate;
Be provided with the fluorion aqueous solution in the described cathode compartment, its component and content are: the Potassium monofluoride of 5～15g/L, matt salt, Sodium tetrafluoroborate or Neutral ammonium fluoride.
Described anion-exchange membrane is OH
-, BF
4 -And F
-Negatively charged ion sees through film, as, NeoseptaACM, NeoseptaAM-1 etc.
Described cationic exchange membrane is H
+, K
+And Na
+The cation permeation film, as, perfluor yellow acid type cationic exchange membrane Nafion450, Nafion324 or MC3470 etc.
The present invention relates to the method for oxidation of above-mentioned electrolyzer, may further comprise the steps:
The first step, pending magnesium alloy workpiece is positioned in the anolyte compartment and with counter electrode is positioned in the cathode compartment, connect the positive pole of power supply, connect the negative pole of power supply as the counter electrode of negative electrode as the anodic magnesium alloy workpiece;
Described counter electrode is the negative electrode that erosion resistance stainless steel or titanium alloy screen frame are processed, and this counter electrode is close to the ion-exchange membrane setting.
Second step, energized and under effect of electric field; Negatively charged ion in the cathode compartment sees through anion-exchange membrane and arrives as in anodic magnesium alloy work-piece surface and the anolyte compartment other and move to the negatively charged ion acting in conjunction of magnesium alloy work-piece surface, at Mg alloy surface formation oxidation film layer.
Cation permeation cationic exchange membrane in the 3rd step, the anolyte compartment arrives cathode compartment, realizes oxidizing process.
Ion-exchange membrane electrolyzer of the present invention is applicable to surperficial anode (differential of the arc or the plasma electrolysis liquid) oxidation processing technique of all magnesiumalloy.
Description of drawings
Fig. 1 is a structural principle synoptic diagram of the present invention;
Fig. 2 is a top view of the present invention;
Fig. 3 is the screen frame synoptic diagram;
Fig. 4 is ion-exchange membrane assembling synoptic diagram;
Among the figure: 1,2 for being equipped with the partition wall of anion-exchange membrane; 3,4 for being equipped with the partition wall of cationic exchange membrane; 5 for treating the magnesium alloy workpiece of oxidation, i.e. anode; 6 is square electrolyzer; 7 use power supply for oxidation; 8 is cable; 9 is the counter electrode as negative electrode, promptly tightly centers on the erosion resistance stainless steel or the titanium alloy screen frame of ion-exchange membrane; 10 is the anolyte compartment; 11 is cathode compartment; 12 and 14 for to manufacture electrolyzer and the used macromolecular material of ion-exchange membrane partition wall, for example, and Vilaterm (PE), SE (PVC) or other polymer architecture material; 13 is anion-exchange membrane or cationic exchange membrane; 15 is the plastics screw; 16 is plastic cap nut; 17 are the cathode chamber solution outlet; 18 are the cathode chamber solution inlet; 19 are anolyte compartment's solution inlet; 20 is anolyte compartment's taphole; Two Room all are equipped with circulation filter respectively, and anticathode electrolyte solution and anodolyte solution carry out circulating filtration and stirring respectively.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
As shown in Figure 1, present embodiment comprises: cathode compartment 11 and the anolyte compartment 10 that places cathode compartment 11 inside, wherein: be provided with electrolyte solution between anolyte compartment 10 and the cathode compartment 11, described cathode compartment 11 is rectangular configuration with anolyte compartment 10.
Four sidewalls of described anolyte compartment 10 are provided with ion-exchange membrane 13 as partition wall, and this ion-exchange membrane 13 comprises: the anion-exchange membrane 13 and the cationic exchange membrane 13 that are oppositely arranged in twos.
Be provided with electrolyte solution in the described anolyte compartment 10, the component of this electrolyte solution and content are: potassium pyrophosphate or the trisodium phosphate of the water glass of the Pottasium Hydroxide of 5～25g/L or sodium hydroxide, 2～25g/L, the sodium metaaluminate of 5～20g/L and 2～10g/L.
Be provided with the fluorion aqueous solution in the described cathode compartment 11, its component and content are: the Potassium monofluoride of 5～15g/L, matt salt, Sodium tetrafluoroborate or Neutral ammonium fluoride.
Described anion-exchange membrane 13 is OH
-, BF
4 -And F
-Negatively charged ion sees through film, and described cationic exchange membrane 13 is H
+, K
+And Na
+The cation permeation film.
Following anodic oxidation of magnetism alloy embodiment all adopts above-described ion-exchange membrane electrolyzer and mode of operation thereof to carry out oxide treatment.
Embodiment one
The AZ91 magnesiumalloy being carried out alkali cleaning in the basic soln of following composition, pass through cleanup acid treatment then, is that the electrolyte solution formed of water is as anodolyte solution with oxidation potassium 6g/L, potassium silicate 18g/L, potassium pyrophosphate 6g/L, surplus at last.
The component of described basic soln is: sodium hydroxide 50g/L, sodium phosphate 10g/L, wetting agent 1g/L;
Described cleanup acid treatment is meant: adopt in the solution that contains phosphoric acid (85%wt.) 380ml/l, sulfuric acid (98%wt.) 16ml/l and water 600ml/l and wash;
With the electrolyte solution of following composition as anodolyte solution:
Pottasium Hydroxide (KOH) 10g/L
Water glass (Na
2SiO
3) 20g/L
Potassium pyrophosphate (K
4P
2O
7) 8g/L
All the other are pure water;
With the electrolyte solution of following composition as catholyte solution:
Potassium monofluoride (KF) 6g/L;
All the other are pure water;
Concrete oxidation operation adopts ion-exchange membrane electrolyzer method for oxidation of the present invention, and step is following:
The first step, pending magnesium alloy workpiece is positioned in the anolyte compartment and with counter electrode is positioned in the cathode compartment, connect the positive pole of power supply, connect the negative pole of power supply as the counter electrode of negative electrode as the anodic magnesium alloy workpiece;
Described counter electrode is the negative electrode that erosion resistance stainless steel or titanium alloy screen frame are processed, and this counter electrode is close to the ion-exchange membrane setting.
Second step, energized and under effect of electric field; Negatively charged ion in the cathode compartment sees through anion-exchange membrane and arrives as in anodic magnesium alloy work-piece surface and the anolyte compartment other and move to the negatively charged ion acting in conjunction of magnesium alloy work-piece surface, at Mg alloy surface formation oxidation film layer.
Cation permeation cationic exchange membrane in the 3rd step, the anolyte compartment arrives cathode compartment.
The current density that anodic oxidation is adopted is 1A/cm
2, oxidization time is 5min..Can on magnesium alloy workpiece 5, obtain uniform and smooth oxidation film layer.
Embodiment two
Adopt the solution of example one to carry out alkali cleaning and pickling in the AZ31 magnesiumalloy.
After the pickling, with the electrolyte solution of following composition as anodolyte solution.
Pottasium Hydroxide (KOH) 10g/L
Sodium metaaluminate (NaAlO
2) 15g/L
Potassium pyrophosphate (K
4P
2O
7) 2g/L
All the other are pure water
With the electrolyte solution of following composition as anodolyte solution:
Matt salt (NH
4HF
2) 8g/L;
All the other are pure water
The oxidation operation step is identical with embodiment one.
The current density that anodic oxidation is adopted is 0.8A/cm
2, oxidization time is 8min..Can on magnesium alloy workpiece 5, obtain uniform and smooth oxidation film layer.
Embodiment three
Adopt the solution of example one to carry out alkali cleaning and pickling magnesium-rare earth (Mg-Nd-Zn-Zr for example, perhaps Mg-Gd-Y etc.).
After the pickling, with the electrolyte solution of following composition as anodolyte solution:
Sodium hydroxide (NaOH) 6g/L
Potassium silicate (K
2SiO
3) 17g/L
Potassium pyrophosphate (K
4P
2O
7) 4g/L
All the other are pure water
With the electrolyte solution of following composition as anodolyte solution:
Sodium tetrafluoroborate (NaBF
4) 8g/L
All the other are pure water
The current density that anodic oxidation is adopted is 1.2A/cm
2, oxidization time is 10min..Can on magnesium alloy workpiece 5, obtain uniform and smooth oxidation film layer.
The oxidation operation step is identical with embodiment one.
Embodiment four
With AM60, ZK60 or ZK40 magnesiumalloy adopt the solution of example one to carry out alkali cleaning and pickling.
After the pickling, with the electrolyte solution of following composition as anodolyte solution:
Pottasium Hydroxide (KOH) 4g/L
Water glass (Na
2SiO
3) 20g/L
Trisodium phosphate (Na
4P
2O
7) 8g/L
All the other are pure water
With the electrolyte solution of following composition as anodolyte solution:
Matt salt (NH
4HF
2) 8g/L
All the other are pure water
The oxidation operation step is identical with embodiment one.
The current density that anodic oxidation is adopted is 0.8A/cm
2, oxidization time is 5min..Can on magnesium alloy workpiece 5, obtain uniform and smooth oxidation film layer.
Compare with document described in the background technology; Adopt present method not only to solve when the magnesiumalloy oxidation contains silicate, aluminate and villiaumite simultaneously with electrolyte solution; Electrolyte solution can produce silicofluoride and fluoaluminate deposition gradually; Thereby cause the electrolyte solution instability until the problem that lost efficacy, and control cathode chamber and the electrolyte components of anolyte compartment and the current density of concentration and oxidation employing thereof very neatly, the height of pH value also needn't be restricted.Apply different current densities and oxidization time and can obtain the oxidation film layer of thickness on magnesium-aluminum series alloy, magnesium-Zn based alloy and magnesium-rare earth-based alloy surface at 5-40 μ m; Its corrosion resistance nature and wear-resistant drag all can reach the prior art performance index.Be sull after the sealing of hole aftertreatment, neutral salt spray test can reach 700 hours 10 grades.Load is 1.0kg, is the wearing test of CS-17 to emery wheel, and before metallic matrix appearred in wearing and tearing, the wear-out period can reach for 2000 weeks at least.
Claims (3)
1. ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy; Comprise: the anolyte compartment that cathode compartment is inner with placing cathode compartment; Wherein: the anolyte compartment is provided with anolyte compartment's electrolyte solution, cathode compartment is provided with the cathode compartment electrolyte solution; Described cathode compartment and anolyte compartment are rectangular configuration, it is characterized in that:
Four sidewalls of described anolyte compartment are provided with ion-exchange membrane as partition wall, and this ion-exchange membrane comprises: anion-exchange membrane that is oppositely arranged in twos and cationic exchange membrane;
Described anion-exchange membrane is 0H
-, BF
4 -And F
-Negatively charged ion sees through film, and described cationic exchange membrane is H
+, K
+And Na
+The cation permeation film;
The component and the content of described anolyte compartment electrolyte solution are: potassium pyrophosphate or the trisodium phosphate of the water glass of the Pottasium Hydroxide of 5～25g/L or sodium hydroxide, 2～25g/L, the sodium metaaluminate of 5～20g/L and 2～10g/L;
Described cathode compartment electrolyte solution is the fluorion aqueous solution, and its component and content are: the Potassium monofluoride of 5～15g/L, matt salt, Sodium tetrafluoroborate or Neutral ammonium fluoride.
2. an anodic oxidation of magnetism alloy method that adopts the ion-exchange membrane electrolyzer of claim 1 is characterized in that, may further comprise the steps:
The first step, pending magnesium alloy workpiece is positioned in the anolyte compartment and with counter electrode is positioned in the cathode compartment, connect the positive pole of power supply, connect the negative pole of power supply as the counter electrode of negative electrode as the anodic magnesium alloy workpiece;
Second step, energized and under effect of electric field; Negatively charged ion in the cathode compartment sees through anion-exchange membrane and arrives as in anodic magnesium alloy work-piece surface and the anolyte compartment other and move to the negatively charged ion acting in conjunction of magnesium alloy work-piece surface, at Mg alloy surface formation oxidation film layer;
Cation permeation cationic exchange membrane in the 3rd step, the anolyte compartment arrives cathode compartment;
Realize the magnesiumalloy oxidizing process.
3. method for oxidation according to claim 2 is characterized in that, described counter electrode is the negative electrode that erosion resistance stainless steel or titanium alloy screen frame are processed, and this counter electrode is close to the ion-exchange membrane setting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102577496A CN101928976B (en) | 2010-08-20 | 2010-08-20 | Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102577496A CN101928976B (en) | 2010-08-20 | 2010-08-20 | Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101928976A CN101928976A (en) | 2010-12-29 |
| CN101928976B true CN101928976B (en) | 2012-05-30 |
Family
ID=43368390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102577496A Active CN101928976B (en) | 2010-08-20 | 2010-08-20 | Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101928976B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703947B (en) * | 2012-05-23 | 2015-09-30 | 上海飞机制造有限公司 | Differential arc oxidation ion-exchange membrane electrolyzer tank liquor replenishment method |
| CN104313664B (en) * | 2014-09-30 | 2017-05-17 | 扬州大学 | Surface treatment method for rare earth magnesium alloy product |
| CN107287641B (en) * | 2016-03-31 | 2019-04-19 | 比亚迪股份有限公司 | A kind of method of anodic oxidation of magnetism alloy liquid, preparation method and anodic oxidation of magnetism alloy |
| CN110606593A (en) * | 2018-06-14 | 2019-12-24 | 深圳安吉尔饮水产业集团有限公司 | Water purification method and system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495267B1 (en) * | 2001-10-04 | 2002-12-17 | Briggs & Stratton Corporation | Anodized magnesium or magnesium alloy piston and method for manufacturing the same |
| CN1405361A (en) * | 2002-10-31 | 2003-03-26 | 上海交通大学 | Magnesium alloy ultrasonic anode oxidation method |
-
2010
- 2010-08-20 CN CN2010102577496A patent/CN101928976B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495267B1 (en) * | 2001-10-04 | 2002-12-17 | Briggs & Stratton Corporation | Anodized magnesium or magnesium alloy piston and method for manufacturing the same |
| CN1405361A (en) * | 2002-10-31 | 2003-03-26 | 上海交通大学 | Magnesium alloy ultrasonic anode oxidation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101928976A (en) | 2010-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1997777B (en) | Method of anodizing metallic surfaces and compositions | |
| CN101608332B (en) | Aluminum alloy with micro-arc oxide ceramic membrane on surface and preparation method thereof | |
| CN101928976B (en) | Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof | |
| CN106884191B (en) | Electrolyte for micro-arc oxidation, micro-arc oxidation method and application | |
| CN103320833A (en) | Anode oxidation dyeing method for metal work-piece | |
| KR20000011380A (en) | Method for forming phosphate film on the steel wires and apparatus used therefore | |
| CN108930055A (en) | Metal-surface nano Coating Processes | |
| US5258109A (en) | Electrodialytic conversion of complexes and salts of metal cations | |
| CN101113529B (en) | Magnesium radical micro arc oxidization electrolytic solution and its micro arc oxidation process | |
| CN102002729A (en) | Copper-containing waste etching solution treatment method and etching solution regeneration method | |
| CN105324520B (en) | The manufacture method of magnesium alloy product | |
| CN111926331A (en) | Alkaline etching solution and in-situ electrolysis copper extraction recycling device and method thereof | |
| CN103409785B (en) | A kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment | |
| CN102787346B (en) | Plasma cleaning process before clean and environment-friendly plated film | |
| Park et al. | Effect of AC current density on the PEO film formation of Al6061 alloy | |
| CN102703947B (en) | Differential arc oxidation ion-exchange membrane electrolyzer tank liquor replenishment method | |
| CN102653877A (en) | Electrolyte for anodic oxidation treatment of magnesium alloy and treatment method thereof | |
| CN106637334B (en) | A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film | |
| CN212770968U (en) | Alkaline etching solution in-situ electrolysis copper extraction recycling device | |
| WO2001092604A3 (en) | Electrolysis cell for restoring the concentration of metal ions in processes of electroplating | |
| CN100381615C (en) | Two-step pigmenting method for green oxidation film layer on magnesium alloy surface | |
| RU2481425C2 (en) | Method of cleaning chromium plating electrolytes | |
| DE19962672A1 (en) | (Re)generation of peroxodisulfate, useful as polymerization initiator or pickle, oxidant or bleach in chemical, metal-working or electronics industry, uses two-part cell divided by combined microporous and anion exchange membranes | |
| EP2401422A2 (en) | Method and device for regenerating peroxodisulfate pickling solution | |
| CN110408936A (en) | A kind of method of electrolytic circuit board acidic etching waste liquor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20101229 Assignee: Jiangsu Jizhong automobile new Mstar Technology Ltd Assignor: Shanghai Jiao Tong University Contract record no.: 2013320010015 Denomination of invention: Ion exchange membrane electrolytic bath for anodic oxidation of magnetism alloy and oxidation method thereof Granted publication date: 20120530 License type: Common License Record date: 20130305 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |