CN102443756A - Method for preparing magnesium alloy - Google Patents
Method for preparing magnesium alloy Download PDFInfo
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- CN102443756A CN102443756A CN2011103628146A CN201110362814A CN102443756A CN 102443756 A CN102443756 A CN 102443756A CN 2011103628146 A CN2011103628146 A CN 2011103628146A CN 201110362814 A CN201110362814 A CN 201110362814A CN 102443756 A CN102443756 A CN 102443756A
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Abstract
The invention discloses a method for preparing magnesium alloy. The method has the advantages of easy operation, no pollution, and low cost, is suitable for batch production, and basically does not change the shape and dimension of the magnesium alloy. The prepared magnesium alloy according to the method has stable coating, good reproducibility, firm combination with a matrix, high surface hardness, wear resistance, and corrosion resistance. According to the method, an oxide film is formed on the surface of the magnesium alloy by using light-heat-chemical effect of laser, surface colouration of the magnesium alloy is realized by the interference from intrinsic color of the oxide and the film, and simultaneously a large area of curved surface or plane color magnesium alloy is prepared by using a rotary laser head through continuously changing laser technological parameters and modulating the facular energy.
Description
Technical field
The present invention relates to the material surface modifying field, relate to a kind of method for preparing magnesiumalloy particularly.
Background technology
Magnesium alloy plate is an Aeronautics and Astronautics industry indispensable material.Economic benefit that the aeronautical material loss of weight brings and improved performance are very significantly; Commercial aircraft and automobile loss of weight equal in quality bring fuel cost to save; The former is nearly 100 times of the latter; And the saving of the fuel oil of fighter expense is nearly 10 times of commercial aircraft, the more important thing is that its maneuvering characteristics improvement can greatly improve its fighting capacity and viability.Just because of this, aircraft industry just can be adopted various measures increases the magnesiumalloy application.Now the used aluminum of aircraft accounts for 85% of aircraft gross weight, and HS, corrosion resistant magnesium alloy plate are better than aluminium sheet performance, uses aboard more to have superiority.
Magnesiumalloy is to alleviate the weaponry quality, realizes the weaponry lightweight, improves the ideal structure material of weaponry each item tactical qualities.Use on the military project, all will use in a large number like vertiplane, fighter plane; Tank, panzer, military jeeps, firearms weapon or the like can make individual soldier's integrated combat system drop to 6.37Kg.Make cartridge case, gun shell with the magnesium plate, the load of individual soldier's bullet is doubled.
Use on the vehicles, like automobile, train, boats and ships etc., weight reduction, the saving energy, minimizing are polluted, and country just greatly develops.Widespread use on 3C Product.On power supply, use, the magnesium power source products all is the pollution-free power supply of high energy, as making Mg-Mn dried battery, magnesium gas battery, Magnesium sea water battery, torpedo power supply and power cell.The high-potential sacrificial magnesium alloy anode plate is used in the metal protection.
Civilian also very wide.Like environment-friendly architecture ornament sheet material, physical culture, medicine equipment, instrument, senior spectacle frame, watch case, senior travel goods etc.
Domestic colored magnesiumalloy production is in the starting stage at present; Relevant according to domestic periodical; Many technical problems still are in the discussion conceptual phase; On colorize method, mostly adopt Chemical Converting Film of Magnesium Alloys, can be divided into: chromate, organic acid system, phosphate-based, KMnO4 system, REE system and stannate system etc. by solution.Chemical conversion film is thin, soft, and is a little less than the protective capacities, general only as decorating or the protective layer middle layer.
Anodic oxidation can obtain than better wear-resistant, the corrosion resistant paint-based undercoat of chemical conversion, and has performances such as good bonding force, electrical insulating property and heat shock resistance concurrently, is one of magnesiumalloy process for treating surface commonly used.And colloidal sol becomes branch to make film forming speed occur interimly increasing fast with slowly, but do not influence the X-ray diffraction phase structure of rete basically.But the fragility of anode oxide film is big, porous, on complex part, is difficult to obtain uniform oxidation film layer.Metallic coating is handled, and magnesium and magnesiumalloy are the most difficult metals that plates, and its reason is following: the Natural manganese dioxide that (1) Mg alloy surface very easily forms, and easy-clear is unclean, has a strong impact on binding force of cladding material; (2) electrochemical activity of magnesium is too high, and all acidic baths all can cause the rapid corrosion of magnesium matrix, or very strong with the replacement(metathesis)reaction of other metals ion, and the coating after the displacement combines very loose; (3) plating or electroless plating are the surface treatment methods that obtains superior solidity to corrosion and electricity, electromagnetism and decorate properties simultaneously; Shortcoming is that Cr, F and the plating bath environmental pollution in the pre-treatment is serious; Majority contains heavy metal element in the coating, has increased the difficulty and the cost that reclaim.Because the characteristic of magnesium matrix also needs to improve to bonding force.
Summary of the invention
For overcoming the defective of prior art; The technical problem that the present invention will solve has provided the method for preparing magnesiumalloy that a kind of easy handling, green non-pollution, cost are low, be suitable for producing in batches, not changing basically the shape and size of magnesiumalloy,, rich color stable, favorable reproducibility through the magnesium alloy coating that this method makes, firm with matrix bond, surface hardness is high, wear resistant corrosion resistant.
Technical scheme of the present invention is: this method for preparing magnesiumalloy; Utilize the light-heat-chemistry effect of laser to generate sull in the Mg alloy surface oxidation; Make magnesium alloy surface coloring jointly through the color of oxide compound itself and the interference effect of film; Through the change of continuous laser processing parameter and the modulation of light spot energy, adopt rotating laser head to prepare large-area curved surface or the colored magnesiumalloy of planar simultaneously.
Owing to adopt above method; The shape and size that so easy handling, green non-pollution, cost be low, be suitable for producing in batches, not changing basically magnesiumalloy, and the magnesium alloy coating that makes through this method is stable, rich color, favorable reproducibility, firm with matrix bond, surface hardness is high, wear resistant corrosion resistant.
Embodiment
Do further detailed description in the face of technical scheme of the present invention down.
This method for preparing magnesiumalloy; Utilize the light-heat-chemistry effect of laser to generate sull in the Mg alloy surface oxidation; Make magnesium alloy surface coloring jointly through the color of oxide compound itself and the interference effect of film; Through the change of continuous laser processing parameter and the modulation of light spot energy, adopt rotating laser head to prepare large-area curved surface or the colored magnesiumalloy of planar simultaneously.
Preferably, this method for preparing magnesiumalloy may further comprise the steps:
(1) magnesiumalloy after will cutting adopts 40 ℃ of nitric acid to carry out pickling 1min, cleans 3min-5min with clear water then, takes out back rapid drying in warm air;
(2) on will being placed on by the maglev worktable of computer control linear quadratic through the magnesiumalloy after step (1) is handled; Adopt various laser technical parameterses and table speed to carry out the laser oxidation coloring large-area treatment, obtain to have the Mg alloy surface sull of different colours through the light-heat-chemistry effect of laser;
(3) the colored magnesiumalloy after step (2) processing is used alcohol wash 5min-10min in 15 ℃-75 ℃ UW, make the large-area colour magnesiumalloy.
Preferably, the computer-controlled moving speed of table of described Z-W is 1mm/s-40mm/s, and continuous laser power is 35W-550W; The laser rectangular light spot is of a size of 0.2mm * 1.31mm-5mm * 7mm; Lasing time 0.5s-7s, defocusing amount 0.01mm-15mm, hot spot overlapping rate 5%-70%.
Preferably, described laser apparatus adopts continuous wave laser, and it is 0.5L/min-5L/min that oxygen adopts coaxial conveying and oxygen flow, or directly adopts airborne oxygen.
Preferably, described laser facula is the rectangular light spot of modulation back energy even.
Preferably, described oxide on surface film is the oxidate compound film that single oxide film or various oxide compound constitute.
Preferably, described magnesiumalloy is the magnesium alloy materials of Mg-AL-Zn-Mn system.
The method that the present invention proposes; Its principle is: through changing the speed of Mg alloy surface roughness, laser technical parameters or worktable; After the continuous laser oxidation, obtain the sull of different oxidation thing (oxide compounds of Mg, AL, Ti, Fe, Cu etc.) and different thickness; Be that the Mg alloy surface sull is the oxidate compound film that double oxide film or various oxide compound constitute, the existence of laminated film makes Mg alloy surface demonstrate more colourful color.The color of Mg alloy surface is that the color and the different thickness sull that form oxide compound after being handled by continuous laser form through the interference of light effect jointly.Can know according to the interference of light principle; Under the situation that does not change oxide film thickness, if the composition of surface oxide film changes, the color of oxide compound self can change on the one hand; Also can change its specific refractory power on the other hand, thereby the color after the interference is also changed.If do not change the surface oxidation film component, and only change oxide thickness, also can therefore present distinct colors.The composition of above oxide film and the thickness of oxide film all wait and realize through changing laser technical parameters (power, spot size, defocusing amount, action time and hot spot overlapping rate etc.), adopt special rotating laser head to prepare large-area curved surface or planar coloured magnesiumalloy simultaneously.
Below be embodiments of the invention:
Embodiment 1:
1, step
1) magnesiumalloy after will cutting adopts 40 degree nitric acid to carry out pickling 1min, cleans 3.5min with clear water then, takes out back rapid drying in warm air;
2) magnesiumalloy after step 1) is handled is placed on the computer-controlled worktable of Z-W; In oxygen flow is the environment of 0.7L/min, carrying out laser oxidation coloring handles: the computer-controlled moving speed of table of Z-W is 3mm/s, and continuous laser power is 80W, and the laser rectangular light spot is of a size of 1mmXlmm; The lasing time is ls; Defocusing amount is 0.01mm, and hot spot overlapping rate 30% obtains blue-black Mg alloy surface sull;
3) with step 2) colored magnesiumalloy after handling use alcohol wash 6min in 35 ℃ UW, take out rapid drying in warm air afterwards, makes clean, stable colored magnesiumalloy.
2, performance
1) adopt scratch method to measure the bonding properties of magnesium alloy surface coloring film and matrix, foundation is with reference to standard GB 5270-85.
2) adopt HXD-1000 type microhardness tester to test colored Mg alloy surface microhardness, experiment load is 500g, and the loading time is 10s.The surface microhardness test is that laser oxidation coloring is handled the back at five points of the different local parallel equidistant tests of colored Mg alloy surface, averages, and the result is as shown in table 1.
Table 1
| Color | Thickness | Bonding force | Microhardness |
| Bluish-green | 15pm | Qualified | 215HV0.2 |
Embodiment 2:
1, step
1) magnesiumalloy after will cutting adopts 40 degree nitric acid to carry out pickling 1min, cleans 5min with clear water then, takes out back rapid drying in warm air;
2) stainless being placed on the computer-controlled worktable of Z-W that will be after step 1) is handled; In oxygen flow is the environment of 2L/min, carrying out laser oxidation coloring handles: the computer-controlled moving speed of table of X_Y is 5mm/s, and continuous laser power is 180W, and the laser rectangular light spot is of a size of 1.2mmXlmm; The lasing time is 1.5s; Defocusing amount is 4.5mm, and hot spot overlapping rate 60% obtains flavous Mg alloy surface sull;
3) with step 2) colored magnesiumalloy after handling use alcohol wash 5min in 55 ℃ UW, take out back rapid drying in warm air, make clean, stablize, high performance colored magnesiumalloy.
2, performance
The bonding properties of magnesium alloy surface coloring film and matrix and micro-hardness testing method are with embodiment 1, and the result is as shown in table 2.
Table 2
| Color | Thickness | Bonding force | Microhardness |
| Golden yellow | 15pm | Qualified | 236HV0.2 |
Embodiment 3:
1, step
1) magnesiumalloy after will cutting adopts 40 degree nitric acid to carry out pickling 1min, cleans 3.5min with clear water then, takes out back rapid drying in warm air;
2) magnesiumalloy after step 1) is handled is placed on the computer-controlled worktable of Z-W; In oxygen flow is the environment of 2.6L/min, carrying out laser oxidation coloring handles: the computer-controlled moving speed of table of X_Y is 30mm/s, and continuous laser power is 450W, and the laser rectangular light spot is of a size of 1mmX2.5mm; The lasing time is 4s; Defocusing amount 6mm, hot spot overlapping rate 55% obtains bright-coloured mauve Mg alloy surface sull;
3) with step 2) colored magnesiumalloy after handling use alcohol wash 20min in 40 ℃ UW, take out back rapid drying in warm air, make clean, stablize, high performance colored magnesiumalloy.
2, performance
The bonding properties of magnesium alloy surface coloring film and matrix and micro-hardness testing method are with embodiment 1, and the result is as shown in table 3.
Table 3
| Color | Thickness | Bonding force | Microhardness |
| Purplish red | 21pm | Qualified | 278HV0.2 |
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs to the protection domain of technical scheme of the present invention to any simple modification, equivalent variations and modification that above embodiment did.
Claims (7)
1. method for preparing magnesiumalloy; It is characterized in that: utilize the light-heat-chemistry effect of laser to generate sull in the Mg alloy surface oxidation; Make magnesium alloy surface coloring jointly through the color of oxide compound itself and the interference effect of film; Through the change of continuous laser processing parameter and the modulation of light spot energy, adopt rotating laser head to prepare large-area curved surface or the colored magnesiumalloy of planar simultaneously.
2. the method for preparing magnesiumalloy according to claim 1 is characterized in that: may further comprise the steps:
(1) magnesiumalloy after will cutting adopts 40 ℃ of nitric acid to carry out pickling 1min, cleans 3min-5min with clear water then, takes out back rapid drying in warm air;
(2) on will being placed on by the maglev worktable of computer control linear quadratic through the magnesiumalloy after step (1) is handled; Adopt various laser technical parameterses and table speed to carry out the laser oxidation coloring large-area treatment, obtain to have the Mg alloy surface sull of different colours through the light-heat-chemistry effect of laser;
(3) the colored magnesiumalloy after step (2) processing is used alcohol wash 5min-10min in 15 ℃-75 ℃ UW, make the large-area colour magnesiumalloy.
3. the method for preparing magnesiumalloy according to claim 2; It is characterized in that: the computer-controlled moving speed of table of described Z-W is 1mm/s-40mm/s; Continuous laser power is 35W-550W, and the laser rectangular light spot is of a size of 0.2mm * 1.31mm-5mm * 7mm, lasing time 0.5s-7s; Defocusing amount 0.01mm-15mm, hot spot overlapping rate 5%-70%.
4. the method for preparing magnesiumalloy according to claim 2 is characterized in that: described laser apparatus adopts continuous wave laser, and it is 0.5L/min-5L/min that oxygen adopts coaxial conveying and oxygen flow, or directly adopts airborne oxygen.
5. the method for preparing magnesiumalloy according to claim 2 is characterized in that: described laser facula is the rectangular light spot of modulation back energy even.
6. the method for preparing magnesiumalloy according to claim 2 is characterized in that: described oxide on surface film is the oxidate compound film that single oxide film or various oxide compound constitute.
7. the method for preparing magnesiumalloy according to claim 2 is characterized in that: described magnesiumalloy is the magnesium alloy materials of Mg-AL-Zn-Mn system.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105603280A (en) * | 2014-10-29 | 2016-05-25 | 中国石油化工股份有限公司 | Fracturing magnesium alloy pressure holding ball and preparation method thereof |
| CN105624671A (en) * | 2015-03-20 | 2016-06-01 | 酷派软件技术（深圳）有限公司 | Preparation method for alloy ceramic film, mobile terminal shell and mobile terminal |
| CN109652786A (en) * | 2019-01-21 | 2019-04-19 | 南京航空航天大学 | A kind of color method and device based on metal material surface dye technology |
| CN111481739A (en) * | 2020-05-18 | 2020-08-04 | 东莞立德生物医疗有限公司 | Biomedical degradable magnesium alloy material and preparation method thereof |
| CN115198226A (en) * | 2022-08-16 | 2022-10-18 | 中国人民解放军空军工程大学 | Method for improving metal corrosion resistance based on femtosecond laser induced surface oxidation layer |
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| CN101693986A (en) * | 2009-10-19 | 2010-04-14 | 江苏大学 | Process for preparing compact thick protection layers on magnesium alloy surfaces |
| CN101775570A (en) * | 2010-02-09 | 2010-07-14 | 江苏大学 | Method for preparing large-area high-performance color stainless steel by laser oxidation coloring |
| CN101787523A (en) * | 2010-03-17 | 2010-07-28 | 上海大学 | Magnesium alloy surface coloring method |
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| CN101348929A (en) * | 2008-08-29 | 2009-01-21 | 上海工程技术大学 | Method for modifying metallic material local surface |
| CN101693986A (en) * | 2009-10-19 | 2010-04-14 | 江苏大学 | Process for preparing compact thick protection layers on magnesium alloy surfaces |
| CN101775570A (en) * | 2010-02-09 | 2010-07-14 | 江苏大学 | Method for preparing large-area high-performance color stainless steel by laser oxidation coloring |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603280A (en) * | 2014-10-29 | 2016-05-25 | 中国石油化工股份有限公司 | Fracturing magnesium alloy pressure holding ball and preparation method thereof |
| CN105603280B (en) * | 2014-10-29 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of pressure break is built the pressure ball and preparation method with magnesium alloy |
| CN105624671A (en) * | 2015-03-20 | 2016-06-01 | 酷派软件技术（深圳）有限公司 | Preparation method for alloy ceramic film, mobile terminal shell and mobile terminal |
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| CN109652786A (en) * | 2019-01-21 | 2019-04-19 | 南京航空航天大学 | A kind of color method and device based on metal material surface dye technology |
| CN111481739A (en) * | 2020-05-18 | 2020-08-04 | 东莞立德生物医疗有限公司 | Biomedical degradable magnesium alloy material and preparation method thereof |
| CN115198226A (en) * | 2022-08-16 | 2022-10-18 | 中国人民解放军空军工程大学 | Method for improving metal corrosion resistance based on femtosecond laser induced surface oxidation layer |
| CN115198226B (en) * | 2022-08-16 | 2023-08-22 | 中国人民解放军空军工程大学 | Method for improving corrosion resistance of metal based on femtosecond laser induced surface oxide layer |
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Application publication date: 20120509 |