CN101629287B - Magnesium alloy surface treatment process - Google Patents
Magnesium alloy surface treatment process Download PDFInfo
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- CN101629287B CN101629287B CN2009101015925A CN200910101592A CN101629287B CN 101629287 B CN101629287 B CN 101629287B CN 2009101015925 A CN2009101015925 A CN 2009101015925A CN 200910101592 A CN200910101592 A CN 200910101592A CN 101629287 B CN101629287 B CN 101629287B
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Abstract
The invention relates to a magnesium alloy surface treatment process which comprises the following steps: (1) soaking and coating phosphate film-forming solution on the surface of a magnesium alloy matrix, washing by water and drying to generate a layer of transition films; and (2) externally coating non-chromate Dacromet coating to obtain a protective coating, wherein the phosphate film-forming solution is sn aqueous solution comprising the following components in concentration: 20-45 g/L of phosphoric acid; 2-4.5 g/L of zinc oxide, 1-4.5 g/L of sodium fluoride, 0.5-2 g/L of ammonium fluoride, 0.5-3 g/L of crystallization controlling agent, 0.5-2 g/L of reaction promoting agent and 0.5-2 g/L of anion surface active agent; the crystallization controlling agent is selected from molybdate or rare-earth salt, and the reaction promoting agent is selected from nitrate or chlorate. The corrosion resistance of the processed magnesium alloy surface is effectively improved.
Description
(1) technical field
The present invention relates to a kind of magnesium alloy surface treatment process.
(2) background technology
21 century, resource and environment have become the matter of utmost importance of human kind sustainable development.Along with the appearance of the develop rapidly of the rapid rising of metallic substance consumption and science and technology, large-scale production process be extensive use of, make the resource dilution day by day of earth watchcase.Some metallic substance-iron, aluminium, copper, lead, zinc etc. continue to use super only century-old again, or even decades.This will give consumption of natural resource is cost, and traditional manufacturing of bearing huge environmental stress proposes higher requirement.Therefore, reducing environmental pollution and save earth limited resources, and then realize human Sustainable development, is the very important and urgent subject of of facing of current people.Aspect the metallic substance resource, magnesium and alloy thereof will become the valuable source of field Sustainable developments such as 21 century communication, automobile, electronics, electrical equipment, aerospace, defence and military, traffic, the energy.
Current, in the research and application and development of magnesium alloy materials, at the very active characteristics of magnesium elements, the key technical problem of being badly in need of solving is: oxidizing fire very easily in the melting and the course of processing, and the production difficulty is very big; Solidity to corrosion is poor; Hot strength, the creep property of existing goods are lower, are restricted in the application of high temperature (150～350 ℃) occasion; Ambient temperature mechanical properties, particularly intensity and plasticity and toughness need to improve.Wherein because the chemical stability of magnesium is low, electropotential is born (E
0=-2.37V), the corrosion stability of magnesium alloy is relatively poor, and this has limited its application to a great extent.Especially very easily corrode on the surface of magnesium alloy in wet environment.The etching problem and its surface property of raising that how to solve magnesium alloy are the key issues of its application prospect of decision, so surface treatment becomes one of most important gordian technique in the magnesium alloy materials application and development.
Present existing Mg alloy surface is handled, and mainly finishes by chemical surface treatment and physical surface modification.Chemical surface treatment mainly is two kinds of chromate treating and bonderizing, its advantage be simple to operate, equipment is cheap.But because the Cr in the chromate treating
6+Harmful, environmental pollution is serious, according to the WEEE of European Union instruction, RoHS instruction and EuP instruction, just eliminated gradually.Bonderizing can not be separately as the protective layer of magnesium alloy, can only be as the short-term between manufacturing procedure bottom before the antirust or japanning; The physical surface modification mainly is technology such as differential arc oxidation, application and plasma spraying.The application techniques of magnesium alloy wherein, corrosive medium penetrates the micropore of coating easily in the atmosphere of humidity, has reduced application layer bonding force and solidity to corrosion.Problems such as differential arc oxidation treatment technology and plasma spraying technology not only cost an arm and a leg, and are difficult to control but also exist processing quality, and coating and its bonding force are not ideal.Therefore along with the magnesium alloy materials application development, need research and develop a kind of new magnesium alloy surface treatment, both effective to protection against corrosion and raising surface property, environmental protection again, economical again.
There is trial to prepare one deck by bonderizing at present and has good protective transformation of energy (transition) membrane technique at Mg alloy surface.At present both at home and abroad phosphating process mainly adopt phosphoric acid salt-permanganate system, zinc be phosphate system obtain with Mg
3(PO
4)
2Or Zn
3(PO
4)
24H
2O is the phosphatize phosphate coat of main component.A kind of magnesium alloy phosphating solution and phosphating process thereof are disclosed as Chinese patent CN1598055.Magnesium alloy phosphating solution, be the aqueous solution that is grouped into by following one-tenth, promptly contain in every liter of this solution: zinc oxide 1～4.5 gram, phosphatase 11 0～45 gram, complexing agent sodium tartrate 0～20 gram, promotor SODIUMNITRATE 0.1～6 gram, corrosion inhibitor Sodium Fluoride 0.5～4.5 gram.Its phosphating process flow process is: the magnesium alloy work-piece surface degreasing is also removed oxide film → washing → phosphatization → washing → oven dry; Phosphatization temperature is 15～80 ℃, and the time is 0.1～50 minute.The phosphating process of this invention can obtain on the magnesium alloy component surface that protective value is good, thickness surpasses chromate film, careful uniform phosphate conversion film.This film is stable, strong adhesion, erosion resistance and the work-ing life that can improve the magnesium alloy component; Stable being easy to of phosphating process controlled, and cost is low.In the magnesium alloy phosphating film film process that conventional art makes, α is mutually only as the micro anode dissolving, and phosphatize phosphate coat " is only gone up forming core at β " or " nucleus that has only β to go up mutually just can be grown up " mutually, spreads after β phase forming core is grown up to grow into alpha phase zone.Magnesium alloy spreads to alpha phase zone by the β phase composite of most α phase (accounting for about 80%) and small portion after β phase forming core is grown up, and film formation time long (30-40 minute), the rete microstructure is comparatively thick and rete is inner that crackle arranged.
Chinese patent CN 1786091 discloses a kind of magnesium alloy non-chromium dacro solution paint and production method thereof, the nano-powder of handling with organosilicon, through nano dispersion fluid, be distributed in the resin of various kinds of resin polymerization crosslinking, it is carried out modification, make Chrome-free, environmental protection with zinc powder and aluminium powder, the magnesium alloy non-chromium dacro solution paint of thin, the salt spray resistance of filming, acidproof, alkaline-resisting, shock resistance, strong adhesion, good weatherability.This invention product has not only kept original Dacroment not produce waste residue, waste gas, sewage, non-environmental-pollution, outside the characteristics such as stronger erosion resistance, thermotolerance, no hydrogen embrittlement, characteristics such as its acid-and base-resisting burn into salt spray resistance, strong adhesion, coating hardness height have been given prominence to more, be a kind of aqueous, environmental protective, energy-conservation Chrome-free system, especially it is anticorrosion to have height, the performance of low thickness.Non-chromium dacro solution paint makes magnesium alloy parts obtain practical value.
(3) summary of the invention
Technical problem to be solved by this invention provides a kind of magnesium alloy surface treatment process that can form the good corrosion protection coating of erosion resistance at Mg alloy surface.
A kind of magnesium alloy surface treatment process, described process of surface treatment comprise (1) earlier with magnesium alloy matrix surface dip-coating phosphoric acid salt film-forming soln, washing then, dry and generate one deck transition film; (2) be coated with the chromium-free Dyclo functional paint outward again and obtain protective coating;
The aqueous solution that described phosphoric acid salt film-forming soln is made up of the component of following concentration:
Phosphoric acid 20～45g/L
Sodium Fluoride 1～4.5g/L
Fluoride amine 0.5～2g/L
Crystal controlling agent 0.5～3g/L
Reaction promotor 0.5～2g/L
Anion surfactant 0.5～2g/L;
Described crystal controlling agent is selected from molybdate or rare-earth salts, and described reaction promotor is selected from nitrate or oxymuriate.
Preferably, described anion surfactant is selected from one of following or more than one arbitrary combination: m-nitrobenzene sodium sulfonate, Sodium dodecylbenzene sulfonate, organic amine.
Preferably, described crystal controlling agent is a Sodium orthomolybdate.
Preferably, described reaction promotor is a SODIUMNITRATE.
Preferably, described chromium-free Dyclo functional paint is made by following method:
A, impregnating material, solid support material and coupling agent are distributed in the organic solvent and obtain the matrix material solvent, then the matrix material solvent is added in the crosslinked good compound resin, heat up and also stir;
B, in zinc powder and aluminium powder, add organosilicon, carry out the coating pre-treatment;
C, pretreated zinc powder and aluminium powder joined in the compound resin stir, add defoamer, flow agent and deionized water, adjust pH value, filtration promptly gets the chromium-free Dyclo functional paint.
Preferably, described impregnating material is selected from one of the following: nickel, silicon-dioxide, chromic oxide, diamond/carbon composite particles, titanium dioxide, zinc oxide, aluminum oxide.
Preferably, described solid support material is a deionized water.
Among the present invention, molybdate or rare-earth salts are mainly used to control phosphoric acid salt and zinc particulate crystalline orientation in the rete as crystal controlling agent.Molybdate such as Sodium orthomolybdate, ammonium molybdate, magnesium molybdate etc.The applicant discovers that the interface behavior between magnesium alloy transition film and the protective coating is bigger to the over-all properties influence of magnesium alloy protective layer.The transition film of this project is by multiple phosphoric acid salt and zinc granulometric composition, because transition film is the phosphatize phosphate coat of reaction growth on magnesium alloy substrate, so is that chemical bond combines between transition film and the magnesium alloy, and bonding force is good; And be physical bond between transition film and the protective coating, bonding force is relatively poor, occurs easily that protective coating can not evenly adhere to or coating phenomenon such as shrink after applying, and bonding force is poor.The present invention is by adjusting the processing parameter controlling diaphragm laminar surface phosphoric acid salt (Zn such as concentration of crystal controlling agent (as molybdate) in the phosphoric acid salt film-forming soln
3(PO
4)
24H
2O) crystalline orientation transfers (020) face (2 θ=9.60 °) (as shown in Figure 4) to by (311) face (2 θ=31.3 °) gradually, make transition film form zig-zag transverse section microtexture, improved nano and micro relief, make the mutual wedging of transition film and protective coating, increase the interface contact area, thereby effectively improved bonding force between transition film and the protective coating, and then improved the over-all properties of magnesium alloy protective layer.
Nitrate of the present invention and oxymuriate are the promotor of reaction, can make that local pH raises rapidly between solution and interface, improve film forming speed.
The present invention adopts anion surfactants such as m-nitrobenzene sodium sulfonate, Sodium dodecylbenzene sulfonate to be adsorbed on the micro anode district (α phase) of magnesium alloy, changed traditional conversion film growth mechanism of magnesium alloy phosphating film " only going up mutually at β could forming core " or " nucleus that has only β to go up mutually just can be grown up ", make part micro anode district become the micro cathode district, increased ratio of cathodic to anodic area, increase the forming core point of phosphatize phosphate coat, improved film forming speed.The absorption of anion surfactant is should partly changing micro cathode (only surplus sub-fraction α keeps electrochemical reaction as micro anode) into mutually as micro anode dissolved magnesium alloy α in reaction, α is gone up mutually also can forming core.Under this control of shifting to new management mechanisms, magnesium alloy immerses just to go up mutually with most α mutually at β after 1 second in the phosphoric acid salt film-forming soln and forms about 2 * 10 simultaneously
5Individual/cm
2The phosphoric acid salt nucleus makes the grain structure of magnesium alloy conversion film obtain tangible refinement, forms many zinc particles in the micro cathode district of α phase simultaneously, just obtains the orderly conversion film of uniform and delicate crystalline structure in 30 seconds.Simultaneously,, avoided formation to be easy to generate the big dissolve area of stress concentration and big film forming district, thereby reduced the internal stress of film, therefore suppressed the generation of tiny crack because the increase of forming core particle makes the dissolving zone of α phase magnesium become many tiny microcells.
Beneficial effect of the present invention is:
(1) adopt anion surfactant to be adsorbed on the micro anode district (α phase) of magnesium alloy, make part micro anode district become the micro cathode district, increased ratio of cathodic to anodic area, increased the forming core point of film forming initial stage phosphatize phosphate coat, improved film forming speed, form the Mg alloy surface transition film of even compact, excellent property, effectively improved corrosion resistance of magnesium alloy;
(2) adopt the chromium-free Dyclo coating technology, solved traditional chromium Dacroment coating technology that contains and had Cr
6+Cr in deleterious environmental issue and the coating
6+Make the acid corrosion-resistant performance of the Dacroment coating problem that descends greatly after the stripping, improved the magnesium alloy acid-resistant corrosion;
(3) by adjusting the processing parameters such as concentration of crystal controlling agent, make transition film form zig-zag transverse section microtexture, improved nano and micro relief, improve the transition film wettability, make the mutual wedging of transition film and protective coating, increase the interface contact area, thereby effectively improved bonding force between transition film and the protective coating, and then improved the over-all properties of magnesium alloy protective coating.
(4) description of drawings
Fig. 1 is the micro-structure diagram that magnesium alloy of the present invention obtains behind process of surface treatment.
Fig. 2 is the surface topography map that adopts the transition film of traditional technology preparation.
Fig. 3 is the surface topography map that adopts the transition film of process of surface treatment preparation of the present invention.
Fig. 4 adds different concns crystal controlling agent (Na among the present invention
2MoO
4) the XRD figure spectrum of the transition film that forms of phosphoric acid salt film-forming soln.
(5) embodiment
Below by embodiment the present invention is made preferably specific description, but protection scope of the present invention is not limited to this.
A kind of magnesium alloy surface treatment process, described process of surface treatment comprise (1) earlier with magnesium alloy matrix surface 1 dip-coating phosphoric acid salt film-forming soln, washing then, dry and generate one deck transition film 2; (2) be coated with the chromium-free Dyclo functional paint outward again and obtain protective coating 3;
The aqueous solution that described phosphoric acid salt film-forming soln is made up of the component of following concentration:
Phosphoric acid 30g/L
Zinc oxide 3g/L
Sodium Fluoride 3g/L
Fluoride amine 1.5g/L
Crystal controlling agent 2g/L
Reaction promotor 1.5g/L
Anion surfactant 1.5g/L;
The microtexture that magnesium alloy of the present invention obtains behind process of surface treatment as shown in Figure 1.Adopt process of surface treatment of the present invention preparation transition film surface topography as shown in Figure 3, and adopt the traditional technology preparation transition film surface topography as shown in Figure 2.
Described anion surfactant is selected m-nitrobenzene sodium sulfonate and 1: 1 combination of Sodium dodecylbenzene sulfonate weight ratio for use.Described crystal controlling agent is a Sodium orthomolybdate.Described reaction promotor is a SODIUMNITRATE.
Described chromium-free Dyclo functional paint is made by following method:
A, impregnating material, solid support material and coupling agent are distributed in the organic solvent and obtain the matrix material solvent, then the matrix material solvent is added in the crosslinked good compound resin, heat up and also stir;
B, in zinc powder and aluminium powder, add organosilicon, carry out the coating pre-treatment;
C, pretreated zinc powder and aluminium powder joined in the compound resin stir, add defoamer, flow agent and deionized water, adjust pH value, filtration promptly gets the chromium-free Dyclo functional paint.
Described impregnating material is selected from SiO 2 powder.Described solid support material is a deionized water.
Each raw material consumption of preparation chromium-free Dyclo functional paint can freely be allocated and realized goal of the invention by those skilled in the art, as can be with reference to the consumption of description among the Chinese patent CN 1786091.
Mg alloy surface carries out technology and performance index and detects result such as following table 1 behind process of surface treatment of the present invention:
Table 1
| Index name | Parameter |
| The transition film nucleation rate | r N＞2.0×10 5/cm 2 |
| Transition film is to different barrier material wetting angle | ＜10° |
| Transition film | Has good bonding force between compact and complete flawless and matrix |
| Sticking power after protective coating applies | 100%, reach one-level |
| Protective coating applies the back petrol-resistance | 4h, the coatingsurface no change |
| Protective coating applies the anti-machine oil in back | 48h, the coatingsurface no change |
| Protective coating applies the back acid resistance | 10％H 2SO 4/ 10h, the coatingsurface no change |
| Protective coating applies the back alkali resistance | 10％N aOH/10h, the coatingsurface light discolouration |
| Protective coating applies back salt spray resistance (NSS) | 480 hours, surpass 9 grades |
| Coating VOC content | ＜90g/L |
| Hardness HB | ≥75 |
| Wear resistance (sticking power) (level) | One-level |
| Tensile strength (Mpa) | ≥210 |
Claims (6)
1. magnesium alloy surface treatment process is characterized in that: described process of surface treatment comprises (1) earlier with magnesium alloy matrix surface dip-coating phosphoric acid salt film-forming soln, washing then, dry and generate one deck transition film; (2) be coated with the chromium-free Dyclo functional paint outward again and obtain protective coating;
The aqueous solution that described phosphoric acid salt film-forming soln is made up of the component of following concentration:
Phosphoric acid 20～45g/L
Zinc oxide 2～4.5g/L
Sodium Fluoride 1～4.5g/L
Fluoride amine 0.5～2g/L
Crystal controlling agent 0.5～3g/L
Reaction promotor 0.5～2g/L
Anion surfactant 0.5～2g/L;
Described crystal controlling agent is selected from molybdate or rare-earth salts, and described reaction promotor is selected from nitrate or oxymuriate, and described anion surfactant is selected m-nitrobenzene sodium sulfonate and 1: 1 combination of Sodium dodecylbenzene sulfonate weight ratio for use.
2. according to the magnesium alloy surface treatment process of claim 1, it is characterized in that: described crystal controlling agent is a Sodium orthomolybdate.
3. according to the magnesium alloy surface treatment process of claim 1, it is characterized in that: described reaction promotor is a SODIUMNITRATE.
4. according to the magnesium alloy surface treatment process of claim 1, it is characterized in that: described chromium-free Dyclo functional paint is made by following method:
A, impregnating material, solid support material and coupling agent are distributed in the organic solvent and obtain the matrix material solvent, then the matrix material solvent is added in the crosslinked good compound resin, heat up and also stir;
B, in zinc powder and aluminium powder, add organosilicon, carry out the coating pre-treatment;
C, pretreated zinc powder and aluminium powder joined in the compound resin stir, add defoamer, flow agent and deionized water, adjust pH value, filtration promptly gets the chromium-free Dyclo functional paint.
5. according to the magnesium alloy surface treatment process of claim 4, it is characterized in that: described impregnating material is selected from one of the following: nickel, silicon-dioxide, chromic oxide, diamond/carbon composite particles, titanium dioxide, zinc oxide, aluminum oxide.
6. according to the magnesium alloy surface treatment process of claim 4 or 5, it is characterized in that: described solid support material is a deionized water.
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| CN101629287B true CN101629287B (en) | 2011-03-23 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477526B (en) * | 2010-11-22 | 2015-02-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacture method thereof |
| CN102560461A (en) * | 2012-01-18 | 2012-07-11 | 河北科技大学 | Zirconium and zirconium alloy zinc-manganese composite phosphating solution and phosphating method thereof |
| CN103469282A (en) * | 2013-09-27 | 2013-12-25 | 昆山纯柏精密五金有限公司 | Preprocessing method of magnesium alloy electro-coating technology |
| CN104341867A (en) * | 2014-11-13 | 2015-02-11 | 常熟市星源金属涂层厂 | Anticorrosive metal coating |
| CN105014049B (en) * | 2015-08-04 | 2017-05-24 | 东南大学 | Al2O3-contained paint for aluminum alloy infiltration casting and method for preparing infiltration casting coating through Al2O3-contained paint |
| CN105908130B (en) * | 2016-05-03 | 2018-07-06 | 贵州航天风华精密设备有限公司 | A kind of raising antioxidative method of aluminum alloy surface |
| CN108660448B (en) * | 2018-06-14 | 2020-10-02 | 潍坊学院 | A normal temperature environment-friendly phosphating solution in which nano titanium dioxide participates in film formation and preparation method thereof |
| CN108707885A (en) * | 2018-06-14 | 2018-10-26 | 潍坊学院 | A kind of preparation method of the room temperature environmental protection complex phosphate coating of doped nano titanium dioxide |
| CN108570673A (en) * | 2018-06-14 | 2018-09-25 | 潍坊学院 | A kind of cold-rolled low carbon steel is without nickel without nitrite normal-temperature phosphorizing liquid and its preparation method |
| CN108588697A (en) * | 2018-06-14 | 2018-09-28 | 潍坊学院 | A method of preparing room temperature environmentally-friendly phosphating film on cold-rolled low carbon steel surface |
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|---|---|---|---|---|
| CN1286319A (en) * | 1999-08-25 | 2001-03-07 | 中国科学院福建物质结构研究所二部 | Ordinary-temp phosphonating liquid |
| JP2003171778A (en) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | Method for forming protective film of metal, and protective film of metal |
| CN1598055A (en) * | 2004-08-02 | 2005-03-23 | 吉林大学 | Magnesium alloy phosphorization solution and its phosphorized technology |
| CN1786091A (en) * | 2005-11-14 | 2006-06-14 | 长春吉大化学有限公司 | magnesium alloy non-chromium dacro solution paint and its preparation method |
-
2009
- 2009-08-17 CN CN2009101015925A patent/CN101629287B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286319A (en) * | 1999-08-25 | 2001-03-07 | 中国科学院福建物质结构研究所二部 | Ordinary-temp phosphonating liquid |
| JP2003171778A (en) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | Method for forming protective film of metal, and protective film of metal |
| CN1598055A (en) * | 2004-08-02 | 2005-03-23 | 吉林大学 | Magnesium alloy phosphorization solution and its phosphorized technology |
| CN1786091A (en) * | 2005-11-14 | 2006-06-14 | 长春吉大化学有限公司 | magnesium alloy non-chromium dacro solution paint and its preparation method |
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