CN1598035A - Aluminium zinc series furface corrosion resistant coating structure of aluminium alloy prducts and preparation technology thereof - Google Patents
Aluminium zinc series furface corrosion resistant coating structure of aluminium alloy prducts and preparation technology thereof Download PDFInfo
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- CN1598035A CN1598035A CNA200410040362XA CN200410040362A CN1598035A CN 1598035 A CN1598035 A CN 1598035A CN A200410040362X A CNA200410040362X A CN A200410040362XA CN 200410040362 A CN200410040362 A CN 200410040362A CN 1598035 A CN1598035 A CN 1598035A
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Abstract
An Al-Zn series surface anticorrosion coat structure of magnesium alloy molding product and its preparation technology. It is the structure that Al-Zn series alloy interface layer with thermal spraying on the layer of magnesium alloy underpinning. There axists thermal sprayed Al coat on surface of the Al-Zn series alloy interface layer. The processing steps are the surface of magnesium alloy underpinning layer blasting to clean rubbish and coarsening. The thermal spraying acts as surface coat. Diffusion treatment at low temperature between 200 deg.C-430 deg.C. The between 1hr.-20hr, seal treatment or hull painting treatment. The coat are high intensity and corrosion resistance simple process, and low cost.
Description
Technical field
The invention belongs to the magnesium alloy technical field, the aluminium zinc that is specifically related to magnesium alloy is carried out a kind of magnesium alloy molded product that surface corrosion resistance handles is anticorrosive coating on surface structure and preparation technology.
Background technology
Advantages such as magnesium and magnesium alloy have that density is low, specific tenacity is high, processing welding and damping capacity well reach dimensional stabilizing, cheap and being subject to people's attention and widespread use successfully are applied to fields such as aviation, automobile making and electronics at present.The chemical property of magnesium is very active, and its standard potential has only-2.37V, is that electropotential is minimum in the common metal.Though magnesium also can form the oxide film of protectiveness in air, this film is very crisp, and not fine and close, it is solid to can not show a candle to Process on Aluminum Alloy Oxidation Film, so solidity to corrosion is very poor.This is very restricted Application of Magnesium.
In order to improve the corrosion resistance nature of magnesium alloy, the scientific worker has done number of research projects both at home and abroad, but general anticorrosion surface treatment at present still is traditional surface protection technique, as anodic oxidation treatment, chemical nickel plating, epoxy sealing, paint or enamel etc., these surface treatment coatings are thinner, and solidity to corrosion is subjected to certain limitation, and all there are the problem that is subjected to device size constraints and discharging waste liquor contamination in plating and anodic oxidation.Therefore, countries in the world have been carried out the anodic oxidation of Mg alloy surface plasma micro-arc in succession, laser surface thermal treatment and laser surface alloying and physical vapor deposition, the research of surface treatment method such as chemical vapour deposition or electron beam evaporation, these modern Magnesiumalloy surface modifying technology utilize the equipment advantage can obtain the corrosion resistant coating of surface treatment excellence, but remove micro-arc anodic oxidation simply power supply (require high-voltage and high electric current, the production cost height) in addition, other technologies must be special expensive device or need under exacting terms such as vacuum, to carry out, except that the particular component in high added value fields such as aerospace or military affairs can adopt these technology, the product of other field is difficult to bear high like this cost, so its market outlook have been subjected to certain restriction.
Summary of the invention
The objective of the invention is to the deficiency that anti-corrosion processing exists at existing Mg alloy surface, the aluminium zinc that a kind of magnesium alloy molded product is provided is anticorrosive coating on surface structure and preparation technology, obtain coating thicker, that combination is better, intensity is higher, solidity to corrosion is good at Mg alloy surface, improve the corrosion resistance nature of Mg alloy surface, technology is simple, low cost of manufacture.
The present invention is by the following technical solutions:
Magnesium alloy molded product aluminium zinc provided by the invention is that the anticorrosive coating on surface structure is composed as follows: it at first has magnesium alloy base mateiral layer, being combined with the Al-Zn that forms by thermospray then on this magnesium alloy base mateiral layer is the alloy middle layer, is that the alloy interlayer surfaces also is combined with the Al coating that forms by thermospray at Al-Zn again.
The acquisition technology of this coating structure may further comprise the steps:
At first, carry out the thermospray pre-treatment, promptly adopt sandblast that foreign material and alligatoring are removed in the surface of magnesium alloy base mateiral layer.Because magnesium alloy is very easily oxidized, easily form magnesium oxide on the surface, but this layer magnesium oxide loosens, if pre-treatment is not removed, the Al-Zn that will cause thermospray is that alloy middle layer and basal body binding force reduce, the impurity of matrix surface also will influence the bonding force of spray material and matrix simultaneously, therefore at first need matrix surface is carried out above-mentioned pre-treatment.
Then, be that alloy is as the middle layer with thermal spraying gun at magnesium alloy base mateiral laminar surface thermospray Al-Zn.The reason that designs this middle layer is: 660.24 ℃ of the fusing points of pure Al, and the fusing point of magnesium is 650 ℃, the alloy melting point of aluminium and magnesium is close, again because the magnesium easy firing, think that the deposited and diffusion technique of magnalium causes a bigger difficult problem.And the fusing point of Zn has only 419.5 ℃, Al-Zn, and the fusing point of MgZn and Al-Mg-Zn eutectic is then also low, helps the formation of diffusion layer and the raising of anchoring strength of coating.The adding in this middle layer can be used as gradient material, its when heating easily and matrix form low-melting MgZn, MgZn
2Eutectic simultaneously can form Al-Zn and Al-Mg-Zn ternary eutectic with the Al coating on top layer again, thus this coating because of containing the etch of the alkaline matter in the anti-environment of Zn, acidity in the environment and sulphur and sulfide then lean on the Al coating antiseptic.
Further, be that alloy interlayer surfaces thermospray Al is as top coat at Al-Zn.Aluminium alloy is because the oxide film on surface is very fine and close; has good solidity to corrosion; aluminium and magnesium all belong to light alloy; two kinds of elements have good consistency; and both bonding propertieies are good, therefore form a certain amount of magnalium compound at Mg alloy surface, can improve the surface electrode current potential; reduce the tendency of galvanic corrosion, the matrix magnesium alloy is played a very good protection.
Afterwards, carrying out the low temperature diffusion processing, diffusion temperature is at 200-430 ℃, and decided diffusion time according to demand, at 1-20 hour.Because there is micropore in the aluminium-plated coating on surface, has certain porosity, the O in environment
2-, Cl
-, and SO
2 2-Penetrate the corrosion that these holes will cause magnesium matrix Deng acid ion.If coating is handled through remelting, can eliminate oxide inclusion and hole in the coating, laminate structure becomes homogeneous texture, based on this principle, for the bonding force that improves coating and matrix and make magnalium can fully spread fusion, further improve its solidity to corrosion, the aluminium-plated magnesium alloy product in surface is carried out the low temperature thermodiffusion with regard to needing.The selection of diffusion temperature is mainly according to Mg-Al and Mg-Al-Zn phasor and diffusion theory and definite.When diffusion temperature was high, the diffusion required time was short, and half fusion state can appear in coatingsurface, and coating compactness is good, but the smooth finish on surface can be subjected to certain loss, if thin-wall part, magnesium alloy substrate deforms easily, and part itself is produced detrimentally affect; When diffusion temperature was low, required diffusion time was longer, but surface smoothness is high, and the creep-resistant property of magnesium alloy substrate part itself is secure.Therefore, according to the difference of workpiece service condition, by adjusting the best effect of determining diffusion temperature and obtaining spraying diffusion diffusion time.Cross when low when diffusion temperature, the diffusion required time is oversize, and the unusual difficulty of the generation of binary phase, and the bonding force of coating and matrix can be subjected to very big influence, does not reach the purpose requirement of diffusion.
Further, also can carry out sealing treatment or application processing to product surface.Can adopt the polyurethane epoxy painting brush to be coated with sealing treatment, its objective is as much as possible the hole of coating is sealed, and fill and lead up because of sprayed particle and pile up the pit that produces.This processing can be carried out according to the arrangement of manufactured part military service situation, can carry out after above-mentioned all coating hot-spraying operations are finished, and also can carry out after thermodiffusion.If very smooth need of surface requirements polished after the thermal spraying aluminum, then can not carry out sealing treatment.For work-ing life of prolonging protection system with for consideration attractive in appearance, also can carry out application on the surface and handle.
In this technology, it is the alloy silk that the spray material in middle layer adopts Al-Zn, and to reduce oxidation ratio, wherein Al and Zn content account for about 99% of alloy silk, but all the other are the element or the rare earth element of trace element and thinning microstructure.Al-Zn carries out after the thermospray of alloy middle layer thermospray is preferably in sandblast and finishes immediately, be no more than 4 hours pitch time the longest, too big as ambient air humidity, then can not spray, keep workpiece surface humidity higher more than 3 ℃ than dew-point temperature at least, just can spray.
Remarkable advantage of the present invention is: the high aluminium zinc of corrosion resistance nature that forms the firm metallurgical binding of one deck on the surface of magnesium alloy product is coating, significantly improves the corrosion resistance nature of Mg alloy surface.Technology of the present invention is simple, low cost of manufacture.
By being that the anticorrosive coating on surface structure is carried out thermal shock test and shown that coating and matrix bond are firm to above-mentioned aluminium zinc, substantially exceeded the numerical value that requires of standard code; By hardness test, record the comparable matrix hardness of surface hardness and improve 1/3rd; By the salt air corrosion experiment, quicken the salt air corrosion experimental period and be not less than 1000 hours, do not see corrosion through 3000 hours surfaces, prove aspect erosion resistance, being significantly increased of this structure.
Description of drawings
Fig. 1 is that the aluminium zinc of this magnesium alloy molded product is the coating structure synoptic diagram of anticorrosive coating on surface structure.
Embodiment
Further describe content of the present invention by the following examples.
Embodiment 1:
At first, select pending magnesium alloy workpiece, it is carried out surface preparation, select phosphorus cast iron shot and emergy for use, its granularity is generally 0.5-1.5mm, fouls such as the oxide film on surface and greasy dirt are removed earlier, handled through sand-blast device then, remove profound oxide compound once more with sand paper, make surperficial freshization simultaneously, being convenient to spray zinc-aluminium layer has combination preferably with it.After sandblast finishes, carry out thermal spraying treatment immediately.
Is that alloy is as the middle layer with thermal spraying gun at magnesium alloy base mateiral laminar surface thermospray Al-Zn.Al-Zn is that the alloy intermediate layer material is that Al-Zn is the alloy silk, and wherein Al and Zn content account for about 99% of alloy silk, but all the other are the element or the rare earth element of trace element and thinning microstructure.Adopt thermal spraying gun, processing parameter is: aero operating pressure: oxygen 0.3-0.6MPa; Acetylene 0.07-0.2MPa; Pressurized air 0.5-0.6MPa; Shielding gas 0.2-0.6MPa.
At Al-Zn is that thermal spraying gun spraying Al coating is adopted on only in the alloy middle layer, and processing parameter is: aero operating pressure: oxygen 0.4-0.5MPa; Acetylene 0.07-0.1MPa; Pressurized air 0.5-0.6MPa; Shielding gas 0.3-0.5MPa.Gas consumption is: oxygen 1.7m
3/ h; Acetylene 0.1m
3/ h; Pressurized air 1.2m
3/ min; Shielding gas 1.5m
3/ h.Spray time, the distance of spray gun and workpiece and translational speed can be decided by different workpieces size, shape and coating thickness requirement.
Then, workpiece is put into box-type furnace, be heated to 200-430 ℃, carry out the low temperature thermodiffusion.
At last, workpiece being carried out sealing treatment or application as required handles.
The coating structure that is obtained as shown in Figure 1, among the figure, 1 is magnesium matrix, 2 for Al-Zn is the alloy middle layer, 3 is the Al coating.
Claims (5)
1, a kind of aluminium zinc of magnesium alloy molded product is the anticorrosive coating on surface structure, it is characterized in that: being combined with the Al-Zn that forms by thermospray on magnesium alloy base mateiral layer is the alloy middle layer, is that the alloy interlayer surfaces also is combined with the Al coating that forms by thermospray at Al-Zn.
2, the described magnesium alloy molded product aluminium of preparation claim 1 zinc is the technology of anticorrosive coating on surface, it is characterized in that may further comprise the steps:
(1) at first adopt sandblast that magnesium alloy base mateiral laminar surface is removed foreign material and alligatoring;
(2) thermospray Al-Zn is that alloy is as the middle layer then;
(3) again thermospray Al as top coat;
(4) carry out low temperature diffusion and handle, diffusion temperature is at 200-430 ℃, and decided diffusion time according to demand, at 1-20 hour;
(5) at last product surface is carried out sealing treatment or application processing.
3, technology according to claim 2 is characterized in that: Al-Zn is that the alloy intermediate layer material is that Al-Zn is the alloy silk, and wherein Al and Zn content account for about 99% of alloy silk, but all the other are the element or the rare earth element of trace element and thinning microstructure.
4, according to claim 2 or 3 described technologies, it is characterized in that: thermospray Al-Zn is that the thermospray spray gun is adopted in the alloy middle layer, and processing parameter is: oxygen 0.3-0.6MPa; Acetylene 0.07-0.2MPa; Pressurized air 0.5-0.6MPa; Shielding gas 0.2-0.6MPa.
5, technology according to claim 2 is characterized in that: thermospray Al coating adopts thermal spraying gun, and processing parameter is: aero operating pressure: oxygen 0.4-0.5MPa; Acetylene 0.07-0.1MPa; Pressurized air 0.5-0.6MPa; Shielding gas 0.3-0.5MPa.
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|---|---|---|---|
| CNB200410040362XA CN1306058C (en) | 2004-07-30 | 2004-07-30 | Aluminium zinc series furface corrosion resistant coating structure of aluminium alloy prducts and preparation technology thereof |
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| CNB200410040362XA CN1306058C (en) | 2004-07-30 | 2004-07-30 | Aluminium zinc series furface corrosion resistant coating structure of aluminium alloy prducts and preparation technology thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497741C (en) * | 2005-11-03 | 2009-06-10 | 中国科学院金属研究所 | Method for protecting magnesium alloy |
| CN101906604A (en) * | 2010-07-30 | 2010-12-08 | 江苏中矿大正表面工程技术有限公司 | Rare earth aluminum alloy wire for thermal spraying |
| CN101564916B (en) * | 2009-05-15 | 2012-09-19 | 重庆理工大学 | Magnesium alloy component with a tin stibium aluminum Babbitt alloy coating on the surface and production method thereof |
| CN101760748B (en) * | 2008-12-10 | 2013-05-01 | 通用汽车环球科技运作公司 | Methods of reducing corrosion between magnesium and another metal |
| CN103290350A (en) * | 2013-04-17 | 2013-09-11 | 华为技术有限公司 | Magnesium alloy raw material or product and preparation method for conductive anticorrosive coating thereof |
| CN106591660A (en) * | 2016-12-08 | 2017-04-26 | 钦州太平电子科技有限公司 | Surface coating for AZ91D magnesium alloy and preparation method of surface coating |
| CN109913787A (en) * | 2019-03-08 | 2019-06-21 | 烟台蓝鲸增材有限公司 | A kind of preparation method of the wear resistant corrosion resistant composite coating of metallurgical bonding |
| CN110846662A (en) * | 2019-11-12 | 2020-02-28 | 四川轻化工大学 | Copper/graphene-plated magnesium alloy composite material and preparation method thereof |
| CN114774832A (en) * | 2022-03-18 | 2022-07-22 | 无锡华金喷涂防腐技术服务有限公司 | Hot spraying Zn-Al-Mg alloy coating and preparation method thereof |
| CN115255585A (en) * | 2022-07-21 | 2022-11-01 | 吉林大学 | Aluminum-magnesium dissimilar alloy resistance spot welding method based on electric arc spraying intermediate layer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127306A (en) * | 1994-07-12 | 1996-07-24 | 宇部兴产株式会社 | Creep-resisting, corrosion-resisting magnesium alloy |
| EP0799900A1 (en) * | 1996-04-04 | 1997-10-08 | Hoogovens Aluminium Walzprodukte GmbH | High strength aluminium-magnesium alloy material for large welded structures |
-
2004
- 2004-07-30 CN CNB200410040362XA patent/CN1306058C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497741C (en) * | 2005-11-03 | 2009-06-10 | 中国科学院金属研究所 | Method for protecting magnesium alloy |
| CN101760748B (en) * | 2008-12-10 | 2013-05-01 | 通用汽车环球科技运作公司 | Methods of reducing corrosion between magnesium and another metal |
| CN101564916B (en) * | 2009-05-15 | 2012-09-19 | 重庆理工大学 | Magnesium alloy component with a tin stibium aluminum Babbitt alloy coating on the surface and production method thereof |
| CN101906604A (en) * | 2010-07-30 | 2010-12-08 | 江苏中矿大正表面工程技术有限公司 | Rare earth aluminum alloy wire for thermal spraying |
| CN101906604B (en) * | 2010-07-30 | 2013-01-23 | 江苏中矿大正表面工程技术有限公司 | Rare earth aluminum alloy wire for thermal spraying |
| CN103290350A (en) * | 2013-04-17 | 2013-09-11 | 华为技术有限公司 | Magnesium alloy raw material or product and preparation method for conductive anticorrosive coating thereof |
| CN103290350B (en) * | 2013-04-17 | 2015-12-23 | 华为技术有限公司 | The method of magnesium alloy material or magnesium alloy product and conduction corrosion protection coating thereof |
| CN106591660A (en) * | 2016-12-08 | 2017-04-26 | 钦州太平电子科技有限公司 | Surface coating for AZ91D magnesium alloy and preparation method of surface coating |
| CN109913787A (en) * | 2019-03-08 | 2019-06-21 | 烟台蓝鲸增材有限公司 | A kind of preparation method of the wear resistant corrosion resistant composite coating of metallurgical bonding |
| CN109913787B (en) * | 2019-03-08 | 2021-04-16 | 烟台蓝鲸增材有限公司 | Preparation method of metallurgically bonded wear-resistant corrosion-resistant composite coating |
| CN110846662A (en) * | 2019-11-12 | 2020-02-28 | 四川轻化工大学 | Copper/graphene-plated magnesium alloy composite material and preparation method thereof |
| CN110846662B (en) * | 2019-11-12 | 2021-12-17 | 四川轻化工大学 | Copper/graphene-plated magnesium alloy composite material and preparation method thereof |
| CN114774832A (en) * | 2022-03-18 | 2022-07-22 | 无锡华金喷涂防腐技术服务有限公司 | Hot spraying Zn-Al-Mg alloy coating and preparation method thereof |
| CN114774832B (en) * | 2022-03-18 | 2024-01-30 | 无锡华金喷涂防腐技术服务有限公司 | Hot spraying Zn-Al-Mg alloy coating and preparation method thereof |
| CN115255585A (en) * | 2022-07-21 | 2022-11-01 | 吉林大学 | Aluminum-magnesium dissimilar alloy resistance spot welding method based on electric arc spraying intermediate layer |
| CN115255585B (en) * | 2022-07-21 | 2023-10-20 | 吉林大学 | Arc spraying interlayer-based resistance spot welding method for aluminum-magnesium dissimilar alloy |
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