CN101705513B - Compound additive for magnesium alloy micro-arc oxidation - Google Patents
Compound additive for magnesium alloy micro-arc oxidation Download PDFInfo
- Publication number
- CN101705513B CN101705513B CN 200910229936 CN200910229936A CN101705513B CN 101705513 B CN101705513 B CN 101705513B CN 200910229936 CN200910229936 CN 200910229936 CN 200910229936 A CN200910229936 A CN 200910229936A CN 101705513 B CN101705513 B CN 101705513B
- Authority
- CN
- China
- Prior art keywords
- arc oxidation
- magnesium alloy
- additive
- rare earth
- coupling agent
- 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.)
- Expired - Fee Related
Links
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a compound additive for magnesium alloy micro-arc oxidation, which consists of trivalent rare earth compound, silane coupling agent and multi-component carboxylate, wherein the rare earth compound is one, two or three of cerium nitrate, neodymium nitrate and lanthanum nitrate; the amount of the rare earth compound is 0.1 to 1 percent; the multi-component carboxylate is one or two of tartrate, citrate, phytate, lactate and oxalate; the amount of the multi-component carboxylate is 5 to 20 percent; a coupling-agent additive is silane with an organic functional group; and the amount of the coupling-agent additive is 1 to 8 percent. The compound additive can be used for various alkaline systems of magnesium alloy micro-arc oxidation of silicate, phosphate, aluminate and the like, and can perform magnesium alloy micro-arc oxidation at room temperature after full mixing. Under the same oxidation conditions, micro-arc oxidation film prepared by use of the additive can be soaked in 3.5 percent NaCl solution for 400 hours with no corrosion, and the hardness of the film remains unchanged.
Description
Technical field
The present invention relates to a kind of composite additive, specifically a kind of compound additive for magnesium alloy micro-arc oxidation can increase substantially membranous layer corrosion resistance under identical thicknesses of layers.
Background technology
Differential arc oxidation is a kind of technology at non-ferrous metal (mainly being aluminium, magnesium, titanium and alloy thereof etc.) surface in situ grow oxide ceramic film.Place specific electrolytic solution with processed, utilize electrochemical method, make its surface produce small spark discharge spot, under thermochemistry, plasma body and electrochemical acting in conjunction, at the oxide film of material surface growth in situ one deck pottery.The rete that utilizes this method to obtain is pottery, has good bonding force, hardness and solidity to corrosion preferably.
At present, the micro-arc oxidation process of magnesium alloy still is in development.Chinese patent " improves the treatment solution and the pre-treating process of performance of magnesium alloy differential arc oxidation film layer " (number of patent application 200710017528), adopt two step pretreatment procedures, will under the 400V positive voltage, carry out differential arc oxidation through pretreated magnesium alloy workpiece of two steps.(H.F.Guo such as H.F.Guo, M.Z.An.Growth of ceramic coatings onAZ91D magnesium alloys by micro-arc oxidation in aluminate-fluoride solutionsand evaluation of corrosion resistance[J] .Applied Surface Science, 2005,246 (1-3): 229-238) improve membranous layer corrosion resistance by in basic film forming liquid, adding Potassium monofluoride, (Li Wang such as LiWang, Li Chen, Zongcheng Yan, et al.Effect of potassium fluorideon structure and corrosion resistance of plasma electrolytic oxidation filmsformed on AZ31 magnesium alloy[J] .Journal of Alloys and Compounds, 2009,480 (2): the ceramic membrane solidity to corrosion that studies show that 469-474) increases with the rising of Potassium monofluoride concentration.In former basic electrolyte system, add an amount of additive, as organic amine (Peng Jihua, cross duckweed, Li Wenfang. ionogen is to the influence [J] of magnesium alloy differential arc oxidation surface film tissue and corrosive nature. the China YouSe Acta Metallurgica Sinica, 2007,17 (11): 1860-1864), the compound of aluminium (is looked into health, Wei Xiaowei. additive is to the influence [J] of magnesium alloy differential arc oxidation. sufacing, 2006,35 (4): 56-58), rare earth neodymium salt (Shi Jingwei, Tian Yanwen, Shao Zhongcai. magnesium alloy differential arc oxidation research [J]. material and metallurgical journal, 2006,5 (2): 154-156) wait the solidity to corrosion that also can improve ceramic coating formed by micro-arc oxidation.But the resulting ceramic membrane of these technology is a pottery, is vesicular on the structure, is prone to crackle in rete, under harsh etching condition, needs sealing treatment.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned the deficiencies in the prior art, provide that a kind of composition is simple, prescription rationally, can effectively improve the compound additive for magnesium alloy micro-arc oxidation of rete corrosion resistance nature.This composite additive only needs to be used with water glass or sodium aluminate etc., just can carry out magnesium alloy differential arc oxidation easily and handle.Use contains the differential arc oxidation electrolytic solution of this composite additive, 8～10 microns of thicknesses of layers and without when sealing, rete can be in 3.5%NaCl solution room temperature soak entirely above 400h and signs of corrosion do not occur.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of compound additive for magnesium alloy micro-arc oxidation, it is characterized in that: the aqueous solution that it is made up of rare earth compound, stablizer, coupling agent, wherein, rare earth compound is one or both in cerous nitrate, neodymium nitrate, the lanthanum nitrate, and content is 0.1%～1%; Stablizer is made up of polynary organic carboxylate, and polynary organic carboxylate is one or both in tartrate, Citrate trianion, phytate, lactic acid salt, the oxalate, content 5%～20%; Coupling agent is a silane coupling agent, and content is 1%～8%.
Silane coupling agent involved in the present invention is a kind of water miscible silane that has machine functional group, and organo-functional group can be vinyl, amino, acyloxy, epoxy-functional, but preferably strengthens film performance and the stable epoxy-functional of electrolytic solution.This coupling agent is with-Si (OCH usually
3)
3Or-Si (OC
2H
5)
3Functional group.Silane coupling agent can be β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, 1,2-two (triethoxy is silica-based) ethane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, profit of one in N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan or their mixture.
Composite additive provided by the present invention can be used for the various systems of magnesium alloy differential arc oxidations such as silicate, phosphoric acid salt and aluminate, composite additive is dissolved in the electrolytic solution of differential arc oxidation by 10ml/L～20ml/L, with rare NaOH solution adjust pH is 11～13, at room temperature can carry out the differential arc oxidation of magnesium alloy behind the thorough mixing.Handle 10min under the 400V direct-flow positive voltage, the gained rete is careful smooth, and corrosion does not appear in the anti-3.5%NaCl solution soaking of rete 400h.
The present invention adopts the composite additive of being made up of rare earth compound, polynary organic carboxylate and silane coupling agent, in the micro-arc oxidation process of magnesium alloy, Performance Detection to obtained rete shows, under identical oxidizing process condition (voltage, temperature, time), the time of the anti-3.5%NaCl solution soaking of differential arc oxidation film layer is brought up to 400h by 12h, and the hardness of rete remains unchanged.Against existing technologies, the present invention forms simply, fills a prescription rationally, can effectively improve the rete corrosion resistance nature.
Embodiment
The present invention will be further described below in conjunction with embodiment.
A kind of compound additive for magnesium alloy micro-arc oxidation of the present invention, the aqueous solution that it is made up of rare earth compound, stablizer, coupling agent.
Described rare earth compound is one or both in cerous nitrate, neodymium nitrate, the lanthanum nitrate, and content is 0.1%～1%.Rare earth compound can effectively improve the density of rete, improves the solidity to corrosion of rete with this.
Described stablizer is made up of polynary organic carboxylate, and polynary organic carboxylate is one or both in tartrate, Citrate trianion, phytate, lactic acid salt, the oxalate, content 5%～20%.The polycarboxylate of trace can improve the stability of electrolytic solution well, prolongs the storage and the work-ing life of electrolytic solution.
Described coupling agent is a silane coupling agent, and content is 1%～8%.Silane coupling agent is used for the environment protection chemical film forming of aluminium alloy, magnesium alloy and zinc coating etc.; coupling agent can form the Me-O-Si covalent linkage in the metallic surface; this covalent linkage can make metal base surface generation passivation reaction, not only have excellent antiseptic property, and gained rete hydrophobic nature is strong.Silane coupling agent is applied to the differential arc oxidation electrolytic solution of magnesium alloy, can improves the hydrophobic nature of rete, further improve the solidity to corrosion of rete.
Embodiment 1:
Below for preparing the content of every liter of composite additive desired substance: cerous nitrate 5g, sodium tartrate 60g, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane 20ml.
Additive amount 16ml/L in the electrolytic solution, water glass 6g/L, sodium aluminate 8g/L, pH value 11 is carried out differential arc oxidation under the normal temperature, and differential arc oxidation carries out under the 400V direct-flow positive voltage, treatment time 10min.The gained rete is careful smooth, and black silk or white rust do not appear in the solution of anti-3.5%NaCl soak at room temperature 400h.
Embodiment 2:
Below for preparing the content of every liter of composite additive desired substance: neodymium nitrate 8g, Triammonium citrate 90g, γ-An Bingjisanyiyangjiguiwan 40ml.
Additive amount 12ml/L in the electrolytic solution, water glass 6g/L, sodium aluminate 8g/L, pH value 12 is carried out differential arc oxidation under the normal temperature, and differential arc oxidation carries out under the 400V direct-flow positive voltage, treatment time 10min.The gained rete is careful smooth, and black silk or white rust do not appear in the solution of anti-3.5%NaCl soak at room temperature 420h.
Embodiment 3:
Below for preparing the content of every liter of composite additive desired substance: lanthanum nitrate 10g, sodium phytate 50g, γ-(methacryloxypropyl) propyl trimethoxy silicane 50ml.
Additive amount 12ml/L in the electrolytic solution, water glass 6g/L, sodium aluminate 8g/L, pH value 12 is carried out differential arc oxidation under the normal temperature, and differential arc oxidation carries out under the 400V direct-flow positive voltage, treatment time 10min.The gained rete is careful smooth, and black silk or white rust do not appear in the solution of anti-3.5%NaCl soak at room temperature 450h.
Embodiment 4:
Below for preparing the content of every liter of composite additive desired substance: cerous nitrate 3g, lanthanum nitrate 3g, Sodium.alpha.-hydroxypropionate 100g, vinyltriethoxysilane 80ml.
Additive amount 10ml/L in the electrolytic solution, water glass 6g/L, sodium aluminate 8g/L, pH value 12 is carried out differential arc oxidation under the normal temperature, and differential arc oxidation carries out under the 400V direct-flow positive voltage, treatment time 10min.The gained rete is careful smooth, and black silk or white rust do not appear in the solution of anti-3.5%NaCl soak at room temperature 450h.
Embodiment 5:
Below for preparing the content of every liter of composite additive desired substance: cerous nitrate 3g, neodymium nitrate 2g, sodium oxalate 120g, 1,2-two (triethoxy is silica-based) ethane 70ml.
Additive amount 10ml/L in the electrolytic solution, water glass 6g/L, sodium aluminate 8g/L, pH value 12 is carried out differential arc oxidation under the normal temperature, and differential arc oxidation carries out under the 400V direct-flow positive voltage, treatment time 10min.The gained rete is careful smooth, and black silk or white rust do not appear in the solution of anti-3.5%NaCl soak at room temperature 450h.
Embodiment 6:
Below for preparing the content of every liter of composite additive desired substance: neodymium nitrate 2g, lanthanum nitrate 5g, sodium tartrate 80g, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan 50ml.
Additive amount 10ml/L in the electrolytic solution, water glass 6g/L, sodium aluminate 8g/L, pH value 12 is carried out differential arc oxidation under the normal temperature, and differential arc oxidation carries out under the 400V direct-flow positive voltage, treatment time 10min.The gained rete is careful smooth, and black silk or white rust do not appear in the solution of anti-3.5%NaCl soak at room temperature 420h.
Claims (2)
1. compound additive for magnesium alloy micro-arc oxidation is characterized in that: the aqueous solution that it is made up of rare earth compound, stablizer, coupling agent, and wherein, rare earth compound is one or both in cerous nitrate, neodymium nitrate, the lanthanum nitrate, content is 0.1%～1%; Stablizer is made up of polynary organic carboxylate, and polynary organic carboxylate is one or both of tartrate, Citrate trianion, phytate, lactic acid salt, oxalate, content 5%～20%; Coupling agent is a silane coupling agent, and content is 1%～8%.
2. according to the composite additive of the described magnesium alloy differential arc oxidation of claim 1, it is characterized in that: said silane coupling agent is β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltriethoxysilane, 1,2-two (triethoxy is silica-based) ethane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, a kind of in N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910229936 CN101705513B (en) | 2009-11-04 | 2009-11-04 | Compound additive for magnesium alloy micro-arc oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910229936 CN101705513B (en) | 2009-11-04 | 2009-11-04 | Compound additive for magnesium alloy micro-arc oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101705513A CN101705513A (en) | 2010-05-12 |
| CN101705513B true CN101705513B (en) | 2011-04-20 |
Family
ID=42375762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910229936 Expired - Fee Related CN101705513B (en) | 2009-11-04 | 2009-11-04 | Compound additive for magnesium alloy micro-arc oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101705513B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102808210B (en) * | 2012-08-17 | 2015-04-22 | 宁波市瑞通新材料科技有限公司 | Micro-arc oxidation surface treatment method and product prepared by same |
| CN103173838B (en) * | 2013-04-11 | 2015-07-01 | 江西科技师范大学 | Magnesium alloy micro-arc oxidation electrolyte and micro-arc oxidation method |
| CN103556204B (en) * | 2013-11-04 | 2016-01-13 | 佳木斯大学 | Magnesium surface ultrasonic microarc oxidation-HF-silane coupling agent multistage composite bioactive coating preparation method |
| CN105063722B (en) * | 2015-09-21 | 2017-08-25 | 四川理工学院 | A kind of silane coupler presses down the differential arc oxidation electrolyte solution and differential arc oxidation membrane preparation method of arc |
| CN108588784B (en) * | 2016-05-24 | 2020-06-02 | 江苏理工学院 | Electrolyte for surface treatment of 7075 aluminum alloy |
| CN106947991B (en) * | 2017-03-09 | 2019-02-12 | 山东大学 | A kind of preparation method of aluminum alloy surface wear-and corrosion-resistant anti-thermal shock coating |
| CN112981494A (en) * | 2021-02-08 | 2021-06-18 | 深圳市钧诚精密制造有限公司 | Titanium alloy micro-arc oxidation process with high light absorption rate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003069026A1 (en) * | 2002-02-13 | 2003-08-21 | Universite Pierre Et Marie Curie | Compositions for the treatment of magnesium alloys |
| CN1796613A (en) * | 2004-12-20 | 2006-07-05 | 中国科学院金属研究所 | Element of arc oxidation electrolyte of corrosion resistant magnesium alloy, and method of element of arc oxidation |
| RU2285066C1 (en) * | 2005-05-14 | 2006-10-10 | Анатолий Иванович Мамаев | Electrolyte for forming black ceramic coat on rectifying metals and their alloys; method of forming such coat and coat formed by this method |
| CN101113529A (en) * | 2007-08-24 | 2008-01-30 | 西安交通大学 | Magnesium radical differential arc oxidization electrolytic solution and its differential arc oxidation process |
-
2009
- 2009-11-04 CN CN 200910229936 patent/CN101705513B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003069026A1 (en) * | 2002-02-13 | 2003-08-21 | Universite Pierre Et Marie Curie | Compositions for the treatment of magnesium alloys |
| CN1796613A (en) * | 2004-12-20 | 2006-07-05 | 中国科学院金属研究所 | Element of arc oxidation electrolyte of corrosion resistant magnesium alloy, and method of element of arc oxidation |
| RU2285066C1 (en) * | 2005-05-14 | 2006-10-10 | Анатолий Иванович Мамаев | Electrolyte for forming black ceramic coat on rectifying metals and their alloys; method of forming such coat and coat formed by this method |
| CN101113529A (en) * | 2007-08-24 | 2008-01-30 | 西安交通大学 | Magnesium radical differential arc oxidization electrolytic solution and its differential arc oxidation process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101705513A (en) | 2010-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101705513B (en) | Compound additive for magnesium alloy micro-arc oxidation | |
| CN104233428B (en) | A kind of method improving aluminum or aluminum alloy material surface anode oxide film alkaline resistance properties | |
| CN101871119B (en) | Preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film | |
| CN103360907B (en) | Self-repairing organic coating applied to gathering pipeline and preparation method of self-repairing organic coating | |
| CN103147109A (en) | Method for sealing aluminum alloy micro-arc oxidation film layer | |
| CN107937893B (en) | Environment-friendly passivation solution for aluminum or aluminum alloy and preparation method and treatment process thereof | |
| CN102234800A (en) | Aluminum alloy rare earth passivating liquid taking chlorine salt as accelerator and use method thereof | |
| CN111117309A (en) | Nano sealing agent and preparation method thereof | |
| CN102677039A (en) | Silane/rare-earth composite protective film on aluminum or aluminum alloy surface and preparation method thereof | |
| CN102703763B (en) | Multielement zinc-aluminum alloy wire and manufacturing method thereof | |
| CN104278260B (en) | A kind of silanization treating agent for aluminum alloy surface and preparation method thereof | |
| CN102268707B (en) | Preparation method and application of metal zinc-containing composite silane film | |
| CN102703758B (en) | La-Nd-containing zinc-aluminum alloy wire and production method thereof | |
| CN113122833B (en) | Aluminum alloy passivation method | |
| CN102703777B (en) | Pr-Nd-containing zinc-aluminum alloy wire and manufacturing method thereof | |
| CN106521471A (en) | Aluminum alloy surface environment-friendly film-forming agent and preparation method thereof | |
| CN105256359A (en) | Copper alloy passivation solution and passivation layer preparation method | |
| CN103614757B (en) | A kind of enclosure method of aluminum alloy surface porous-film rare earth | |
| CN116515371B (en) | High-performance aqueous inorganic zinc-rich paint and preparation method and application thereof | |
| CN102605405A (en) | Anodization method for improving protection performance of aluminum and aluminum alloy | |
| CN102703760B (en) | Zinc-aluminum alloy wire containing La, Ce, Pr and Nd and production method thereof | |
| JP5651912B2 (en) | Method for producing resin-coated steel | |
| CN102703780B (en) | Zinc-aluminum alloy wire containing La, Ce and Nd and production method thereof | |
| CN102703759A (en) | La-Ce-containing zinc-aluminum alloy wire and production method thereof | |
| CN102703778B (en) | La-Pr-containing zinc-aluminum alloy wire and manufacturing method thereof |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110420 Termination date: 20131104 |