CN102260424A - Treating fluid for improving corrosion resistance of magnesium alloy surface, preparation method thereof and process thereof - Google Patents
Treating fluid for improving corrosion resistance of magnesium alloy surface, preparation method thereof and process thereof Download PDFInfo
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- CN102260424A CN102260424A CN 201110204357 CN201110204357A CN102260424A CN 102260424 A CN102260424 A CN 102260424A CN 201110204357 CN201110204357 CN 201110204357 CN 201110204357 A CN201110204357 A CN 201110204357A CN 102260424 A CN102260424 A CN 102260424A
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- deionized water
- silane
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Abstract
The invention provides a treating fluid for improving corrosion resistance of a magnesium alloy surface, a preparation method thereof and a process thereof, which are used for protecting the surfaces of various magnesium alloys while a machining gap is short. The treating fluid contains combination of two or more components of a silane coupling agent, rare earth salts, corrosion inhibitor, ethanol and deionized water; the treating fluid mainly comprises 2-15% of silane and 85-98 % of deionized water or ethanol or 4-12% of silane, 4-10% of ethanol and 80-90% of deionized water; and the rest additives account for 1%. The treating fluid is simple, convenient and easy to operate. A treated film layer with thickness of less than 2 microns can be used for resisting environment with temperature of higher than 50 DEG C and humidity of more than 80% for no less than 15 days so that the treated magnesium alloy has no corrosion mark on the surface for 15 days under a high-temperature and high-humidity environment. The corrosion resistant film layer provided by the invention has the characteristics of excellent binding force with an alloy matrix, good high temperature and high humidity resistance and no influence on follow-up machining and surface coating of workpieces.
Description
Technical field
The present invention relates to the surface anticorrosion protection treatment technology between the magnesium alloy manufacturing procedure, be used for the corrosion of anti-hot and humid environment between the magnesium alloy manufacturing procedure, can substitute slushing oil and handle, avoid influencing following process or reduce coating's adhesion.
Background technology
1) etching problem of magnesium alloy
Magnesium alloy is a kind of electropotential extremely low (being commonly used for sacrificial anode material), surface film oxide not fine and close (the PB value is less than 1), and has the metallic substance that minus tolerance is counted effect, so relative other structural metallic materials extreme differences of its corrosion resisting property.Usually magnesium alloy workpiece all will carry out protective treatment in the surface before the sale of dispatching from the factory, wherein the most commonly used is to carry out external coating again after surface passivation or phosphatization or the anodic oxidation, the processing of spraying paint that application is mainly adopted, because magnesium alloy is not acidproof, so can not directly carry out cathode electro-coating as steel part.Passivation or anodic oxidation before the application have anticorrosion ability preferably with chromic salt, but because environmental issue, this surface preparation often is subjected to great restriction.Therefore many novel surface treatment processs have appearred in recent years, as physical vapor deposition, thermospray, plating etc., but these coat preparing technologies mainly are to have good solidity to corrosion in the environment under arms at magnesium alloy workpiece, coating preparation all is a globality on the one hand, coating and matrix have fabulous tack, the technology of preparing relative cost of coating is higher, can not be directly used in the rotproofing of magnesium alloy inter process.
2) storage problem of magnesium alloy inter process
The corrosion resisting property extreme difference of magnesium alloy, when magnesium alloy workpiece when the course of processing is deposited a middle or short term, if do not carry out the protective treatment on surface, evidence of corrosion appears in the just easy oxidation meeting of unsalted surface of exposing because of processing, particularly under the summer high temperature high humidity environment, this phenomenon is even more serious, greatly influences the following process of magnesium alloy member.Utilize treatment process antirust between the steel part manufacturing procedure to be coated with slushing oil at Mg alloy surface, though can prevent the etching problem of magnesium alloy inter process, but slushing oil is impregnated in the hole or kapillary of magnesium alloy easily, follow-up final surface-treated cleaning is caused great obstacle, cause final top coat very easily to peel off for this reason, do not have due effect with matrix.
Though the magnesium alloy inter process can protect by passivation or anodic oxidation or phosphatization, but necessary special surface treatment workshop (chamber) or corresponding work personnel, need to carry out the authentication permission of surperficial environmental administration simultaneously, be difficult to carry out above-mentioned surface treatment for the machine shop that does not possess the respective surfaces processing, can only send special surface treatment department to handle, need repeatedly different sites zone machining for complex parts, it is loaded down with trivial details especially that the surface treatment of this inter process just seems, is badly in need of a kind of technology that just can protect the inter process etching problem at machine shop by simple process.
Summary of the invention
The objective of the invention is to solve corrosive problem between machine shop magnesium alloy manufacturing procedure,, can online convenience carry out antiseptic Technology Mg alloy surface by the rust protection liquid and the working method of invention.
The present invention between the magnesium alloy member manufacturing procedure the preservative solution prescription and be formulated as follows:
A kind of treatment solution that improves surface anticorrosion between the magnesium alloy manufacturing procedure is characterized in that described treatment solution
Contain two or more composition combinations in silane coupling agent, rare-earth salts, inhibiter, ethanol, the deionized water, its main proportioning is:
Silane 2%-15%, deionized water or ethanol 85%-98%;
Perhaps silane 4%-12%, ethanol 4%-10%, deionized water 80%-90%;
All the other additive total amount＜1%.
Further, the silane of described silane coupling agent can be epoxy group(ing), vinyl or amino.
Further, the silane of described silane coupling agent is KH550, KH460, KH450, KH69 or KH27.
The preparation method of above-mentioned treatment solution, described method is as follows:
Single silane coupling agent or two kinds of coupling agents are mixed stirring, join in deionized water or the ethanolic soln, perhaps stir in deionized water and the alcoholic acid mixing solutions, be hydrolyzed afterwards, add the inhibiter and the rare-earth salts of trace after the hydrolysis again.
Surface preservative treatment technique between a kind of raising magnesium alloy manufacturing procedure is characterized in that: the described treatment solution of described process using, and magnesium alloy member to be soaked or brushes, soak time is 30 seconds-2 minutes.
Further, described magnesium alloy member comprises further that also the high bake curing process makes crosslinked with silicane after handling through preservative solution, and temperature is 80-120 ℃, and the time is 10-30 minute.
Further, comprise further that also the alkali lye treatment process makes crosslinked with silicane.
The magnesium alloy wear-resistance film layer of preservative solution of the present invention and preparation has following characteristic:
(1) preservative solution environment-protecting asepsis, treating processes does not have pollution problem, and the preservative solution that adds rare-earth salts has certain self-repair function
(2) Zhi Bei wear-resistance film layer water white transparency, thicknesses of layers＜2 micron, this rete densification has good solidity to corrosion, and than a untreated little order of magnitude, its polarization resistance is than the big 1-2 of a naked magnesium alloy order of magnitude from corrosion electric current density for it.
(3) surface after this handles not only without any negative impact, can increase the bonding force of Mg alloy surface and follow-up organic coating or heat insulating coat to follow-up surface treatment on the contrary.Therefore this inter process rotproofing also can be used as the pretreatment procedure that follow-up coating is handled.
Magnesium alloy inter process processing antirusting treating method of the present invention can be used for the magnesium alloy workpiece of any trade mark, the particularly rotproofing in short-term after the large-scale workpiece partial operation, characteristics with environmental protection, simple and easy to do, strong operability, exemplar after treatment can stand the surface corrosion pit not occur greater than 50 ℃, humidity 80% environment about 20 days.
Description of drawings
Fig. 1 is without the surface topography behind the antiseptic sample humid heat test;
Fig. 2 is the surface topography behind antiseptic sample humid heat test;
Fig. 3 is the corrosion speed figure of AZ31 magnesium alloy sample different treatment.
Embodiment
The present invention at first with the magnesium alloy machined piece through oil removing cleaning, take out after then workpiece being immersed in the rust protection liquid certain hour, put into baking oven baking certain hour, take out and get final product.If workpiece is too big, a workpiece is local machining at every turn, can adopt the brushing mode that surface treatment is carried out in the processing part, to being difficult to the workpiece with the baking oven baking, also can dry or use hot blast drying naturally.
Embodiment 1
The selection size is the distortion AZ31 magnesium alloy of 70 mm * 35mm * 1mm.
The concrete operations step is:
(1) preservative solution configuration: KH550: deionized water: Ce (NO3)
3Be 10:89.9:0.1, will
The material of above-mentioned three kinds of compositions disposes in proportion and stirs static anti-the putting in back, makes its hydrolysis.
(2) sample pretreatment: alkali cleaning oil removing → deionized water rinsing.
(3) rotproofing: cleaned test specimen is put into preservative solution soaked 1 minute, put into baking oven after the taking-up, take out back room temperature placement and get final product 120 ℃ of bakings 30 minutes.
Print after above-mentioned processing and untreated print are tested through polarization of electrode, and the former is 1.28e from corrosion electric current density
-6A/cm
2, the latter is 6.772e
-5A/cm
2, its polarization resistance through the rotproofing and the part that is untreated is respectively: 8.83e
4Ω cm
2, 9.46e
2Ω cm
2
Case study on implementation 2
The selection size is the distortion AZ31 magnesium alloy of 70 mm * 35mm * 1mm
The concrete operations step is:
(1) preservative solution configuration: KH460: the deionized water volume ratio is 8:92, KH460 silane is put into deionized water for stirring in proportion evenly place the back, makes its hydrolysis.
(2) rotproofing: will process the back test piece through the sand papering oil removing, and put into preservative solution after the wiped clean and soaked 30 seconds, and put into baking oven after the taking-up 100 ℃ of bakings 30 minutes, room temperature is placed and is got final product after taking out.
(3) print after above-mentioned processing and untreated print are through quickening damp and hot experiment, in temperature is 60 ℃, humidity〉in 80% the constant water bath box through experiment continuously in 17 days, discovery exemplar surface after treatment is without any corrosion pit, and undressed print has many etch pits (seeing Fig. 1, Fig. 2) in simulation humid heat test rear surface.
Case study on implementation 3
The selection size is the distortion AZ31 magnesium alloy of 70 mm * 35mm * 1mm
The concrete operations step is:
(1) preservative solution configuration: KH69:H
2O:CH
3CH
2OH=2:2:96 puts into deionized water and the ethanolic soln back that stirs in proportion with KH69 silane and places, and makes its hydrolysis.
(2) rotproofing: test piece is put into preservative solution and was soaked 1 minute through the sand papering oil removing after will processing after the wiped clean, dries after the taking-up to get final product.
Naked magnesium alloy and the magnesium alloy print after rotproofing are put into 5%NaCl solution acceleration immersion processing in 5 hours, can find naked magnesium print big area corrosion, and print after treatment has only a spot of corrosion (see figure 3).
Claims (7)
1. a treatment solution that improves surface anticorrosion between the magnesium alloy manufacturing procedure is characterized in that described treatment solution
Contain two or more composition combinations in silane coupling agent, rare-earth salts, inhibiter, ethanol, the deionized water, its main proportioning is:
Silane 2%-15%, deionized water or ethanol 85%-98%;
Perhaps silane 4%-12%, ethanol 4%-10%, deionized water 80%-90%;
All the other additive total amount＜1%.
2. treatment solution according to claim 1 is characterized in that: the silane of described silane coupling agent can
To be epoxy group(ing), vinyl or amino.
3. treatment solution according to claim 2 is characterized in that: the silane of described silane coupling agent is KH550, KH460, KH450, KH69 or KH27.
4. the preparation method of treatment solution according to claim 2, described method is as follows:
Single silane coupling agent or two kinds of coupling agents are mixed stirring, join in deionized water or the ethanolic soln, perhaps stir in deionized water and the alcoholic acid mixing solutions, be hydrolyzed afterwards, add the inhibiter and the rare-earth salts of trace after the hydrolysis again.
5. one kind is improved surface preservative treatment technique between the magnesium alloy manufacturing procedure, it is characterized in that: described process using treatment solution as claimed in claim 1, and magnesium alloy member to be soaked or brushes, soak time is 30 seconds-2 minutes.
6. surface preservative treatment technique between a kind of raising magnesium alloy manufacturing procedure according to claim 4, it is characterized in that: after described magnesium alloy member is handled through preservative solution, comprise further that also the high bake curing process makes crosslinked with silicane, temperature is 80-120 ℃, and the time is 10-30 minute.
7. surface preservative treatment technique between a kind of raising magnesium alloy manufacturing procedure according to claim 4 is characterized in that: comprise further that also the alkali lye treatment process makes crosslinked with silicane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110204357 CN102260424A (en) | 2011-07-21 | 2011-07-21 | Treating fluid for improving corrosion resistance of magnesium alloy surface, preparation method thereof and process thereof |
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|---|---|---|---|
| CN 201110204357 CN102260424A (en) | 2011-07-21 | 2011-07-21 | Treating fluid for improving corrosion resistance of magnesium alloy surface, preparation method thereof and process thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965653A (en) * | 2012-11-01 | 2013-03-13 | 安徽未来表面技术有限公司 | Self-repairing non-phosphorus ceramic processing liquid for galvanized plate and ceramic process thereof |
| CN103045089A (en) * | 2012-12-17 | 2013-04-17 | 青岛研博电子有限公司 | Metal surface aseptic technology |
| CN103214926A (en) * | 2012-12-17 | 2013-07-24 | 青岛中科英泰商用系统有限公司 | Anticorrosion coating material coating technology |
| CN103484016A (en) * | 2013-09-24 | 2014-01-01 | 昆山凯诺尔金属制品有限公司 | Method for processing surface of magnesium product by using D3 organosilicone liquid |
| CN104099021A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Anticorrosion and antibacterial aluminium alloy surface treating agent |
| CN113755097A (en) * | 2021-09-15 | 2021-12-07 | 湖南工程学院 | Surface treating agent for slowing down rust liquid sagging of weathering resistant steel at initial service stage as well as preparation method and use method thereof |
| CN113897616A (en) * | 2021-10-18 | 2022-01-07 | 南京理工大学 | Magnesium alloy surface anticorrosion treatment process |
| CN117567892A (en) * | 2024-01-16 | 2024-02-20 | 东北大学 | Magnesium alloy anticorrosive paint and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58188329A (en) * | 1982-04-26 | 1983-11-02 | Matsushita Electric Ind Co Ltd | Magnetic recording medium |
| CN101717930A (en) * | 2009-12-25 | 2010-06-02 | 华烁科技股份有限公司 | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface |
-
2011
- 2011-07-21 CN CN 201110204357 patent/CN102260424A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58188329A (en) * | 1982-04-26 | 1983-11-02 | Matsushita Electric Ind Co Ltd | Magnetic recording medium |
| CN101717930A (en) * | 2009-12-25 | 2010-06-02 | 华烁科技股份有限公司 | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965653A (en) * | 2012-11-01 | 2013-03-13 | 安徽未来表面技术有限公司 | Self-repairing non-phosphorus ceramic processing liquid for galvanized plate and ceramic process thereof |
| CN103045089A (en) * | 2012-12-17 | 2013-04-17 | 青岛研博电子有限公司 | Metal surface aseptic technology |
| CN103214926A (en) * | 2012-12-17 | 2013-07-24 | 青岛中科英泰商用系统有限公司 | Anticorrosion coating material coating technology |
| CN103484016A (en) * | 2013-09-24 | 2014-01-01 | 昆山凯诺尔金属制品有限公司 | Method for processing surface of magnesium product by using D3 organosilicone liquid |
| CN104099021A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Anticorrosion and antibacterial aluminium alloy surface treating agent |
| CN113755097A (en) * | 2021-09-15 | 2021-12-07 | 湖南工程学院 | Surface treating agent for slowing down rust liquid sagging of weathering resistant steel at initial service stage as well as preparation method and use method thereof |
| CN113897616A (en) * | 2021-10-18 | 2022-01-07 | 南京理工大学 | Magnesium alloy surface anticorrosion treatment process |
| CN117567892A (en) * | 2024-01-16 | 2024-02-20 | 东北大学 | Magnesium alloy anticorrosive paint and preparation method and application thereof |
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Application publication date: 20111130 |