CN1824832A - Surface treatment method of Mg alloy - Google Patents
Surface treatment method of Mg alloy Download PDFInfo
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- CN1824832A CN1824832A CN 200510008809 CN200510008809A CN1824832A CN 1824832 A CN1824832 A CN 1824832A CN 200510008809 CN200510008809 CN 200510008809 CN 200510008809 A CN200510008809 A CN 200510008809A CN 1824832 A CN1824832 A CN 1824832A
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Abstract
This invention relates to magnesium alloy surface processing method, the procedures are that a. it is processed by the mixed solution of hydrofluoric acid and sulfuric acid. b. then it is cleaned by pure water to wash surface residual agent. c. it is processed by hydrofluoric acid. d. then it is washed by pure water to wash surface residual agent. e. it is processed by calcium carbonate water solution, so the magnesium alloy surface processing is finished. In this invention, simple etching solution is used to etch the alloy surface at room temperature to make material surface single face, and put an end of corrosion.
Description
Technical field
The present invention relates to surface treatment method of Mg alloy, adopting result of the present invention is that other of Mg alloy surface removed mutually, and be not to form thin film on the surface, so in removal process, do not need to go especially to remove program, have that heavy metal free pollutes, floride-free (fluorine can damage the ozone layer, also can cause Greenhouse effect) produces, and can effectively increase magnesium alloy erosion resistance, be beneficial to the advantages such as tack of follow-up application.
Background technology
Magnesium enriches in natural standing stock and (occupies 1.93% in the earth's crust, occupy 0.13% in the ocean in addition), be only second to aluminium and iron in structure commonly used in metal, be number three, and the proportion of magnesium alloy is (magnesium proportion 1.8, aluminium 2.7, titanium 4.5, iron 7.9, copper 8.9, zinc 7.1) the lightest in the utility structure alloy.Because the CO of oil crisis and relevant environmental protection
2Eliminate plan, under the considering of lightweight, province's energy and exhaust emission, magnesium alloy is preferable selection.In addition, magnesium has characteristics such as preferable thermal diffusivity, electromagnetic shielding, be applied on the thin-wall workpiece of 3C portable product outer casing member, with plastics or other metallographic phase than more meeting its demand.
In addition the specific gravity capacity of magnesium alloy (Damping capacity) be about aluminium alloy 10-25 doubly, 1.5 times of zinc alloy, show that it has splendid damping capacity, be used in and help to reduce of the interference of external shock source on the portable device inner precise electronic, optical module.In addition, it is gradually high that the requirement of decree is reclaimed in each major country's environmental protection of the world, because magnesium alloy has returnability, and can decompose by natural oxidation under physical environment, that is, being beneficial to environmental protection is the very big advantage of magnesium alloy development.But because magnesium is active big, easily surperficial and oxygen forms loose zone of oxidation and causes erosion resistance not good, therefore, though magnesium is the structure metal of proportion minimum, but still can't be applied to many light-weighted occasions as aluminium alloy.
Many magnesium alloy surface treatment are in order to block aqueous vapor, the oxygen in the atmosphere, to reach the purpose of corrosion protection.At present magnesium alloy surface treatment includes and changes into epithelium processing, anodizing, electroplating processes and metal cover and handle.Change into that epithelium is handled, anodizing is preferable with the effect of chromic salt system, but the waste liquid of chromate treating has the problem in the environmental protection, because sexavalent chrome can be carcinogenic and can be caused the pollution of other form of environment aspect, therefore, community of European Union proposed draft in July, 1997, had completely forbidden chromic use in 2003, and forbid containing the product import of chromium component, and obtained the promise of America and Japan two big industrial advanced states, so chromate treating will be under an embargo.
But at present the product handled of non-chromate is compared with chromate treating still being difficult to aspect corrosion stability and the reliability.At present the TaiWan, China worker grind institute's material at the research of its environmental protection plating bath, as phosphoric acid salt, silicate, manganate and aluminate etc., can avoid the restriction and the forbidding of environmental regulation, reduced environmental impact, but the handling problem of chemical waste fluid is arranged, still more not environmental protection heavy metal (Mn) problem is still arranged, and phosphorus is the element that causes the excellent oxidation of reservoir in the long run.
According to (the American Society for Testing and Materials of American Society Testing and Materials, ASTM) definition, changing into epithelium refers to and utilizes chemistry or electrochemical treatment, make the metallic surface generate a kind of skin membrane that contains this metal ingredient, for example the chromic salt epithelium of zinc is handled, the phosphate coating of iron and steel is handled, the anodizing of aluminium alloy etc., desire is implemented and is changed into the metal that epithelium is handled, the compound of its formation or oxide compound must not have water-soluble, simultaneously neither meal, that is, must be continuous epithelium.
Changing into epithelium need be in its treating processes, treatment solution is imposed a temperature and generates one deck protection epithelium, the about 10-20 microampere of its corrosion current/square centimeter (μ A/cm with Mg alloy surface
2) about, its surface will form some hallrcuts in forming the process of epithelium, makes surperficial homogenizing, as shown in Figure 1, and for manganous phosphate changes into surface topography after the processing; These hallrcuts will be helpful to the sticking power of follow-up application.Shown in Fig. 3 a, traditional way is to grow the epithelium that changes into that contains heavy metal, phosphide by material surface.This layer epithelium is in the process that reclaims again system, to cause adverse influence, make in the molten soup of alloy more impurity element is arranged, so before recovery, must many again programs be peeled off by this epithelium, this will cause the increase of cost recovery, can produce waste liquid more again in addition in stripping process, and environment is caused secondary pollution.
In addition, TaiWan, China TW 573061 patent announcements " aluminiferous used for magnesium alloy chemical synthesis treatment liquid, high anti-corrosion surface treated magnesium alloy product and manufacture method thereof ", wherein disclose a kind of aluminiferous used for magnesium alloy chemical synthesis treatment liquid, high anti-corrosion surface treated magnesium alloy product and manufacture method thereof, can make the high anti-corrosion surface treated magnesium alloy product according to its manufacture method.
TaiWan, China TW 557329 patent announcements " phosphoric acid salt that contains zinc steel plating plate changes into treatment process " disclose a kind of method that can form fine and close zinc phosphate tunicle in the short period of time on the surface that contains the zinc coating steel plate.Reaching the method for above-mentioned purpose, is after making it and the adjustment of note surface contacting with treatment solution down, to carry out the tunicle of general phosphoric acid zinc salt again and handle.Last note divalent or 3 valency metals are Zn, Fe, Mn, Ni, Co, Ca, Mg, Al etc. for example, and its phosphoric acid salt is to contain below the particle diameter 5 μ m and concentration is preferred version with 0.001-30g/L.
TaiWan, China TW 539769 patent announcements " surface treatment tin plate and chemical synthesis treatment liquid ", a kind of surface treatment tin plate is disclosed, also disclose and employedly when obtaining this steel plate contained phosphate ion, tin ion and organosilane coupler, and pH is the chemical synthesis treatment liquid of 1.5-5.5.Surface treatment tin plate does not wherein contain the chromium not good to environment protection, be have good coating adherence, the steel plate of spray paint back solidity to corrosion, resistance to rust and processibility.
TaiWan, China TW 555887 patent announcements " surface treatment method of Mg alloy " disclose a kind of surface treatment method of Mg alloy, mainly may further comprise the steps: a magnesium alloy plate at first is provided; Then this magnesium alloy plate is carried out sandblasting, to remove the impurity on magnesium alloy plate surface; Spray (Arc Spray) fine aluminium on this magnesium alloy plate surface with electric arc then and form the layer of aluminum film; Again this aluminium film is carried out hot-pressing processing, so that the aluminium film is more fine and close.
Comprehensive as can be known above-mentioned, surface of magnesium aluminium alloy of the prior art is handled and is adopted the chromic acid art breading, and following shortcoming is arranged:
1. to environment: heavy chromium metallic wastewater, chromium sludge curing desire to look for buried being difficult for-society and the soil cost is loaded too heavy;
2. to the user: the heavy metal chromium that remains in the accessory surface is separated out, and causes user's context to be subjected to severe contamination.For example notebook computer CPU arithmetic speed is fast more, and chromium is separated out fast more, operation under the closed air conditioner surroundings, and it is big to influence user's health degree.If the design of collocation cooling fan, chromic acid is separated out fast more, spreads also wide more;
3. in addition, in a conventional manner, grow the epithelium that changes into that contains heavy metal, phosphide, can produce heavy metal contamination, fluorine diffusion etc., and fluorine can damage the ozone layer, also can cause Greenhouse effect etc. by the test piece surface.
Find that by former study adding formed second relative its corrosion of different-alloy element in the magnesium alloy has very big influence.Research according to people such as Nadine is pointed out, Mg
17Al
12Containing under the environment of chlorion is inert, therefore the Mg in the system of magnalium
17Al
12Can hinder corrosion.And people such as Das think and eliminate Mg in the alloy
17Al
12Can increase inhibition of corrosion, because they think that the corrosion of magnalium mainly is by α phase and Mg
17Al
12Alternate Jia Fanni effect causes.
This metal is subjected to the trend of environment solution temptation to be called " electrolytic solution tension " (ElectrolyticSolutional tension).The metal that electrolytic solution tension is big, because turn to metal ion easily, thus compare corrosion-vulnerable, on the contrary the little metal of electrolytic solution tension more can not corrode.
The notion of electrolytic solution tension is used on the electrochemistry and is called " Jia Fanni current potential " (Galvanic Potential) or " electrolytic potential " again, is called for short current potential.Different metals has different current potentials, so when two kinds of different metals overlapped, because both potential differences will produce electric current, its principle was as with the situation that The natural flow of water always proceeds from a higher level to a lower one.The result of this battery effect because of pass through (the flowing to negative electrode from anode) of electric current, makes the molten corrosion that disappears of high potential metal generation anode.When potential difference is big more, the electric current of generation is strong more, and the corrosive wear rate is just big more.
In the electrochemistry tagmeme, Jia Fanni galvanic series (Galvanic Potential Series) can illustrate under varying environment the trend of various metal anodes or cathodic.In seawater, fresh water solution or other industrial atmosphere, the Jia Fanni galvanic series also may be variant, with the Jia Fanni galvanic series in the seawater, descending according to the metal current potential with the metal series arrangement, be in regular turn: potassium (K), sodium (Na), magnesium (Mg), aluminium (Al), zinc (Zn), cadmium (Cd), iron (Fe), cobalt (Co), nickel (Ni), tin (Sn), aluminium (Pb), copper (Cu), silver (Ag), platinum (Pt), gold (Au).
This corrosion betides the contact of two kinds of different metals or alloy, and can produce the situation of Jia Fanni battery (Galvanic cell), and the Jia Fanni galvanic series of common metal material in seawater corroded easily than the metal of tool positive polarity.For example: in oceanographic engineering, with scolding tin (Lead-tin alloy) welding brass fittings because the galvanic series of brass relatively has cathodic, so than scolding tin with positive polarity than corrosion-vulnerable.Come comparison from the viewpoint of alloy again, if battery effect occurs on two phase alloys, for example: have ferrite (ferrite) and cementite (cementite) in the steel, then because ferrite relatively has positive polarity, cementite relatively has cathodic, will produce galvanic corrosion, therefore we can say, its corrosion resistibility of two nearly all phase alloys is all than Single Phase Metal difference.
Summary of the invention
The object of the present invention is to provide a kind of surface treatment method of Mg alloy, adopt simple etching solution under the condition of room temperature, etch processes to be carried out on the aluminum magnesium alloy surface, reach and stop the purpose that burn into reduces pollution.
The present invention be with simple etching solution at room temperature the short period of time etching is carried out on magnesium alloy (for example AZ91D) surface, with the Mg on surface
17Al
12Remove mutually with rich aluminium-α (Al-rich-α), make material surface form single phase, stop by α phase, Mg
17Al
12With the Jia Fanni effect caused corrosion of rich aluminium-α (Al-rich-α) between mutually.Find by experimental result, can effectively increase its corrosion stability, and can make the surface reach surfaceness uniformly, be beneficial to the tack of follow-up application.Because result of the present invention is that other of surface removed mutually, and is not to form thin film on the surface, so in removal process, do not need to go especially to remove.
At first, the invention provides a kind of surface treatment method of Mg alloy, its step comprises:
A. earlier via hydrofluoric acid (HF) and sulfuric acid (H
2SO
4) mixing solutions handle;
B. then water cleans, its remained on surface medicament of flush away;
C. again through hydrofluoric acid (HF) solution-treated;
D. water cleaning again after, its remained on surface medicament of flush away;
E. again through lime carbonate (CaCO
3) aqueous solution processing;
Like this, can finish the surface treatment of magnesium alloy.
Wherein, described hydrofluoric acid (HF) and sulfuric acid (H
2SO
4) mixing solutions in, the volumetric ratio of hydrofluoric acid (HF) is 0.05-0.2, sulfuric acid (H
2SO
4) volumetric ratio be 0.02-0.08, water (H
2O) volumetric ratio is 0.4-0.8.The volumetric ratio of hydrofluoric acid (HF) is 0.1-0.3 in described hydrofluoric acid (HF) solution, water (H
2O) volumetric ratio is 0.7-0.9.
In the practical application, the sulfuric acid (H among the present invention
2SO
4) can be the vitriol oil of 95-98%.
Particularly, the invention provides a kind of surface treatment method of Mg alloy, its step comprises:
A. earlier add sulfuric acid (H via hydrofluoric acid (HF)
2SO
4) solution-treated;
Wherein, hydrofluoric acid (HF) adds sulfuric acid (H
2SO
4) solution composition be:
Hydrofluoric acid (HF), sulfuric acid (H
2SO
4) and water (H
2O) volumetric ratio is respectively: hydrofluoric acid: 0.05-0.2, sulfuric acid: 0.02-0.08, water: 0.4-0.8; For example, described hydrofluoric acid adds vitriolic solution and can be: hydrofluoric acid 50-200mL+ sulfuric acid 20-80mL+ water 400-800mL;
B. water cleans again, its remained on surface medicament of flush away;
C. afterwards through hydrofluoric acid (HF) solution-treated;
Described hydrofluoric acid solution consists of:
The volumetric ratio of hydrofluoric acid and water is respectively hydrofluoric acid: 0.1-0.3, water: 0.7-0.9; For example, the solution of described hydrofluoric acid can be: hydrofluoric acid 100-300mL+ water 700-900mL;
D. water cleans again, its remained on surface medicament of flush away;
E. after the calcium carbonate aqueous solution processing;
Like this, can finish the surface treatment of magnesium alloy.
In the surface treatment method of Mg alloy of the present invention, the service temperature that described hydrofluoric acid adds the vitriolic solution-treated is 20-40 ℃, and the time is 1-15 minute.Service temperature during described hydrofluoric acid solution is handled is 20-40 ℃, and the time is 0.5-15 minute.
Surface treatment method of Mg alloy of the present invention can be applied to the AZ91D magnesium alloy, and described AZ91D magnesium alloy is the magnesium alloy that is best suited for the 3C Product shell at present, and it consists of: Al, Zn, Mn, Si, Cu, Fe, Ni and Mg, specifically as shown in Table 1:
The composition of table one, AZ91D magnesium alloy
| Composition | Al | Zn | Mn | Si | Cu | Fe | Ni | Mg |
| wt％ | 8.8 | 0.69 | 0.212 | 0.02 | 0.002 | 0.005 | 0.001 | Balance (Balance) |
Surface treatment method of Mg alloy of the present invention can be applicable to β phase (Mg in the magnesium alloy
17Al
12) with the removal of (Al-rich) mutually of rich aluminium.
In sum, surface treatment method of Mg alloy of the present invention, be with simple etching solution at ambient temperature the short period of time Mg alloy surface is carried out selective etch, make material surface form single phase, and stop the corrosion.The present invention not only can effectively increase the corrosion stability of alloy, and makes material surface possess uniform surfaceness, is beneficial to the tack of follow-up application or baking vanish.Result of the present invention is that other of alloy surface removed mutually, so material surface does not have tradition to change into the heavy metal of processing or the epithelium of phosphide, does not also have the problem of heavy metal waste liquid on treatment process.The present invention has advantages such as heavy metal free pollutes, no fluorochemical is residual simultaneously.
Through the result of long-time various at home and abroad disclosed database retrievals of contriver and inquiry, for surface treatment method of Mg alloy of the present invention, also do not have identical at present both at home and abroad or the similar techniques report, the present invention is very important for industrial community.
Description of drawings
Fig. 1 is the alloy surface pattern of tradition after phosphoric acid changes into processing.
Fig. 2 is the synoptic diagram of the implementation step of surface treatment method of Mg alloy enforcement of the present invention.
Fig. 3 a and Fig. 3 b are tradition and surface treatment method of Mg alloy of the present invention enforcement test piece cross sectional representation relatively, and wherein, Fig. 3 a is for handling the situation that epithelium is handled through changing into, and Fig. 3 b is the [hydrofluoric acid (HF)+sulfuric acid (H through specified proportion
2SO
4)]/situation that hydrofluoric acid (HF) is handled.
Fig. 4 is according to [the hydrofluoric acid (HF)+sulfuric acid (H of surface treatment method of Mg alloy of the present invention through specified proportion
2SO
4)] and hydrofluoric acid (HF) solution-treated after the alloy surface pattern.
Fig. 5 is the [hydrofluoric acid (HF)+sulfuric acid (H through specified proportion
2SO
4)] and hydrofluoric acid (HF) solution-treated before with handle after the synoptic diagram of alloy surface roughness concentration.
Fig. 6 is the [hydrofluoric acid (HF)+sulfuric acid (H through specified proportion
2SO
4)] and hydrofluoric acid (HF) solution-treated before and after polarization curve.
Fig. 7 is the [hydrofluoric acid (HF)+sulfuric acid (H through specified proportion
2SO
4)] and the preceding x-ray diffraction analysis that reaches after handling of hydrofluoric acid (HF) solution-treated.
Fig. 8 is the metallograph of embodiments of the invention after surface treatment and the synoptic diagram of data analysis.
Fig. 9 is the metallograph of embodiments of the invention after surface treatment and the synoptic diagram of data analysis.
Figure 10 is the traditional photo of object before and after surperficial baking vanish.
Figure 11 is the photos of embodiments of the invention before and after surperficial baking vanish.
Figure 12 is a synoptic diagram of the top layer adhesion condition of embodiments of the invention after surface treatment.
Figure 13 is another synoptic diagram of the top layer adhesion condition of embodiments of the invention after surface treatment.
Primary clustering nomenclature among the figure:
1 surface treatment program, 11 hydrofluoric acid+sulfuric acid 12 pure water 13 hydrofluoric acid
14 calcium carbonate aqueous solutions, 2 objects, 21 original surfaces
22 change into epithelium 23 selective etch layer a baking vanish layers
Embodiment
Surface treatment method of Mg alloy of the present invention, its implementing procedure as shown in Figure 2, surface treatment program 1 is earlier via the [hydrofluoric acid (HF)+sulfuric acid (H of specified proportion
2SO
4)] 11 solution-treated (can adopt for example coating, impregnating mode), wash 12 (preferably pure water cleanings) again with water, its remained on surface medicament of flush away; Then, through hydrofluoric acid (HF) 13 solution-treated of specified proportion (can adopt for example coating, impregnating mode are handled), wash 12 (preferred pure water cleans) again with water, its remained on surface medicament of flush away; Material is dried up; Again at lime carbonate (CaCO
3) in the aqueous solution 14, carry out 30 minutes to 60 minutes processing (for example: dipping).
In surface treatment method of Mg alloy of the present invention, described [hydrofluoric acid (HF)+sulfuric acid (H
2SO
4)] 11 solution, wherein the volumetric ratio of each composition is respectively hydrofluoric acid (HF): 0.05-0.2, sulfuric acid (H
2SO
4): 0.02-0.08, water (H
2O): 0.4-0.8; For example, hydrofluoric acid 50-200mL+ sulfuric acid 20-80mL+ water 400-800mL; Service temperature 20-40 ℃, time 1-15 minute (min);
Wherein, above-mentioned most preferred condition is: the volumetric ratio of hydrofluoric acid, sulfuric acid, water is respectively hydrofluoric acid: 0.174, and sulfuric acid: 0.052, water: 0.774; For example, the solution of described [hydrofluoric acid+sulfuric acid] 11 can be hydrofluoric acid 174mL+ sulfuric acid 52mL+ water 774mL; 25 ℃ of service temperatures; 3.5 minutes time.
The solution of described hydrofluoric acid (HF) 13, hydrofluoric acid (HF), water (H
2O) volumetric ratio is respectively hydrofluoric acid: 0.1-0.3, water: 0.7-0.9; Particularly, it consists of: hydrofluoric acid 100-300mL+ water 700-900mL; Service temperature 20-40 ℃, time 0.5-15 minute;
Wherein, above-mentioned most preferred condition is: the ratio of hydrofluoric acid, water is respectively hydrofluoric acid: 0.2, and water: 0.8; For example, hydrofluoric acid 200mL+ water 800mL; 25 ℃ of service temperatures; 3 minutes operating times.
Described lime carbonate (CaCO
3) aqueous solution 14, lime carbonate (CaCO wherein
3) with the ratio of water be 5wt%; For example, lime carbonate (CaCO
3) 5g+ water (H
2O) 100mL; Service temperature: 40 ℃.
Shown in Fig. 3 a, traditional surface treatment mode is that the original surface 21 by object 2 grows the chromic salt that contains heavy metal, phosphide, phosphoric acid salt etc. and changes into epithelium 22; And surface treatment method of Mg alloy of the present invention is by the original surface etching of object 2 material internal of entering, and shown in Fig. 3 b, is selective etch layer 23 of the present invention; Mode of the present invention is with selective etch the out-phase of material surface to be removed, and produces the similar hallrcuts pattern that changes into after epithelium is handled, will be helpful to the sticking power of follow-up application, and this is another advantage of Mg alloy surface facture of the present invention.Magnalium spare is as notebook computer and phone housing etc., and except the die casting equipment of leading portion, it is critical process that the epithelium of back segment is handled, the present invention can be on magnalium spare the coating layer of metal, can be described as environment-protective process, on industry, will replace the chromic acid processing.
Embodiment one
Material is through [hydrofluoric acid (HF)+sulfuric acid (H
2SO
4)] 11 and hydrofluoric acid (HF) 13 solution-treated after, it is similar to the pattern after changing into epithelium to observe its surperficial pattern (please refer to shown in Figure 4) by sweep electron microscope (SEM), so can reach the effect of the sticking power that increases application; And also can reach similar roughness by its surface of measurement (please refer to shown in Figure 5) of surfaceness, in order to follow-up application.Among Fig. 5, Lt: measure length (mm); Lc: per unit length is got a bit (mm); The 1. middle test piece of adopting firm die casting to finish of experiment numbers is without any processing (as-diecast).
Embodiment two
Mg alloy surface facture of the present invention found that via electrochemistry experiment after [hydrofluoric acid+sulfuric acid] 11 and hydrofluoric acid hydrogen 13 solution-treated, its corrosion current can decline to a great extent, and corrosion current can be from about 300 microampere/square centimeter (μ A/cm
2) drop to 10 microampere/square centimeter (μ A/cm
2) below, shown in Fig. 6 and table two.The epithelium that changes into of its result and chromic acid, non-chromic acid series is handled close.
The test piece of table two, enforcement is through [the hydrofluoric acid (HF)+sulfuric acid (H of specified proportion
2SO
4)] and hydrofluoric acid (HF) solution-treated before and after corrosion current relatively.
Surface treatment method of Mg alloy of the present invention is via the analytical results of x-ray diffraction instrument, and as shown in Figure 7,1. symbol represents to adopt firm die casting to finish, compare without the test piece (as-diecast) of any processing among the figure.As can be seen, handle back β phase (Mg through method of the present invention
17Al
12) diffraction peak disappear, make the test piece surface after handling form the structure of single phase; Its corrosion stability increases, and reaches its protection effect.By experimental results show that is to remove β phase (Mg
17Al
12) with rich aluminium (Al-rich) mutually, and do not form one deck epithelium on its surface, therefore on reclaiming, do not need to do in addition again the processing of peeling off.
As shown in Figure 8, for the surface of embodiments of the invention through [hydrofluoric acid (HF)+sulfuric acid (H
2SO
4)] 11 solution-treated is after 3.5 minutes, then metallograph and the data analysis synoptic diagram of the results after hydrofluoric acid (HF) 13 is handled 3 minutes again.The data analysis outcome record of 1,2 two analysis position is in table three among Fig. 8.
Table three, data analysis result (atomic percent)
| | 1 | 2 |
| Mg | 66.66 | 59.43 |
| Al | 6.35 | 8.46 |
| Ca | 0 | 0 |
| F | 26.99 | 32.11 |
| Amount to | 100.00 | 100.00 |
The fluorine content that can be demonstrated material surface by the data analysis in the table three is very high, and fluorine can damage the ozone layer, and also can cause bad consequences such as Greenhouse effect; But heavy metals such as the material surface iron-free of present embodiment, manganese, chromium produce, also without phosphorus generation.
As shown in Figure 9, for the surface of embodiments of the invention through [hydrofluoric acid (HF)+sulfuric acid (H
2SO
4)] 11 solution-treated is after 3.5 minutes, then handles 3 minutes through hydrofluoric acid (HF) 13, and is last, again at lime carbonate (CaCO
3) in the aqueous solution 14, metallograph and the data analysis synoptic diagram of the result after carrying out handling in 30 minutes to 60 minutes; The data analysis outcome record of 1,2 two analysis position is in table four among Fig. 9.
Table four, data analysis result (atomic percent)
| | 1 | 2 |
| Mg | 90.87 | 86.94 |
| Al | 7.25 | 8.26 |
| Ca | 0 | 0.46 |
| F | 1.88 | 4.34 |
| Amount to | 100.00 | 100.00 |
Can demonstrate through lime carbonate (CaCO by the data analysis in the table four
3) after the aqueous solution 14 handles, can significantly reduce its fluorine content; Heavy metals such as the material surface iron-free of present embodiment, manganese, chromium produce, also without phosphorus generation.Wherein, lime carbonate (CaCO in the calcium carbonate aqueous solution
3) with the ratio of water be: 5wt%; For example, its composition can be lime carbonate (CaCO
3) 5g+ water (H
2O) 100mL; Service temperature: 40 ℃.
As shown in figure 10, be the photo of traditional object before and after surperficial baking vanish, wherein, the picture left above and top right plot be traditional object without surperficial baking vanish photograph before, lower-left figure and bottom-right graph are the photo behind surperficial baking vanish; After checking one against another up and down, can find out easily that traditional article surface lacks glossiness, the product attractive in appearance for needs is an important disadvantages.
As shown in figure 11, be the photo of embodiments of the invention before and after surperficial baking vanish; The picture left above and top right plot are embodiment without the photograph before the surperficial baking vanish, and lower-left figure and bottom-right graph are the photo after adding the surperficial baking vanish of lime carbonate; By among the figure after checking one against another up and down, can find out that the object material surface of present embodiment has good glossiness.
As shown in figure 12, for the surface of embodiments of the invention through [hydrofluoric acid (HF)+sulfuric acid (H
2SO
4)] after 11 the solution-treated 3.5 minutes (min), the then synoptic diagram of the top layer adhesion condition after surface treatment after hydrofluoric acid (HF) 13 is handled 3 minutes (min) again; The picture left above shows that the baking vanish of present embodiment faces down, and test piece is down crooked; Top right plot is the front view of present embodiment test piece, and down after the bending, baking vanish layer a still is attached to substrate surface in the test piece that lower-left figure shows embodiment.
As shown in figure 13, for the surface of embodiments of the invention through [hydrofluoric acid (HF)+sulfuric acid (H
2SO
4)] after 11 the solution-treated 3.5 minutes (min), then handle 3 minutes (min) through hydrofluoric acid (HF) 13, last, again at lime carbonate (CaCO
3) the synoptic diagram of top layer adhesion condition after the aqueous solution 14 carries out handling in 30 minutes to 60 minutes, the picture left above shows that the baking vanish of present embodiment faces down, test piece is down crooked; Top right plot is the front view of present embodiment test piece, and lower-left figure shows that the down crooked back of the test piece baking vanish layer a of embodiment still is attached to substrate surface.
From the above, the surface treatment method of magnesium alloy of the present invention can reach following performance requriements: (1) adherence of filming; (2) exposed solidity to corrosion; (3) low-resistance value; (4) do not contain objectionable impuritiess such as chromium.
The use and the embodiment of the Mg alloy surface facture of the invention described above; be one of the preferred embodiments of the present invention; be not in order to limiting to feature of the present invention, the technique means that all the present invention of utilization are correlated with, found the creation again of principle, all should belong in protection scope of the present invention.
Claims (13)
1, a kind of surface treatment method of Mg alloy, its step comprises:
A. handle via hydrofluoric acid and vitriolic mixing solutions earlier;
B. then water cleans, its remained on surface medicament of flush away;
C. handle through hydrofluoric acid solution again;
D. water cleaning again after, its remained on surface medicament of flush away;
E. handle through calcium carbonate aqueous solution again;
Like this, can finish the surface treatment of magnesium alloy.
2, surface treatment method of Mg alloy as claimed in claim 1, wherein, the volumetric ratio of hydrofluoric acid is 0.05-0.2 in described hydrofluoric acid and the vitriolic mixing solutions; The vitriolic volumetric ratio is 0.02-0.08; The volumetric ratio of water is 0.4-0.8.
3, surface treatment method of Mg alloy as claimed in claim 1, wherein, the volumetric ratio of hydrofluoric acid is 0.1-0.3 in the described hydrofluoric acid solution; The volumetric ratio of water is 0.7-0.9.
4, a kind of surface treatment method of Mg alloy, its step comprises:
A. handle via hydrofluoric acid and vitriolic mixing solutions earlier;
Wherein, the volumetric ratio of hydrofluoric acid, sulfuric acid, water is respectively in described hydrofluoric acid and the vitriolic mixing solutions: hydrofluoric acid: 0.05-0.2, sulfuric acid: 0.02-0.08, water: 0.4-0.8;
B. water cleans again, its remained on surface medicament of flush away;
C. handle through hydrofluoric acid solution after;
The volumetric ratio of hydrofluoric acid and water is respectively hydrofluoric acid in the described hydrofluoric acid solution: 0.1-0.3, water: 0.7-0.9;
D. water cleans again, its remained on surface medicament of flush away;
E. after the calcium carbonate aqueous solution processing;
Like this, can finish the surface treatment of magnesium alloy.
5, as claim 1 or 4 described surface treatment method of Mg alloy, wherein, the service temperature that described hydrofluoric acid and sulfuric acid mixed solution are handled is 20-40 ℃, and the time is 1-15 minute.
6, as claim 1 or 4 described surface treatment method of Mg alloy, wherein, the service temperature that described hydrofluoric acid solution is handled is 20-40 ℃, and the time is 0.5-15 minute.
7, a kind of surface treatment method of Mg alloy, its step comprises:
A. handle via hydrofluoric acid and vitriolic mixing solutions earlier;
Wherein, the volumetric ratio of hydrofluoric acid, sulfuric acid, water is respectively hydrofluoric acid in described hydrofluoric acid and the vitriolic mixing solutions: 0.05-0.2, and sulfuric acid: 0.02-0.08, water: 0.4-0.8, and
The service temperature that hydrofluoric acid and sulfuric acid mixed solution are handled is 20-40 ℃, and the time is 1-15 minute;
B. water cleans again, its remained on surface medicament of flush away;
C. then handle through hydrofluoric acid solution;
The volumetric ratio of hydrofluoric acid, water is respectively hydrofluoric acid in the described hydrofluoric acid solution: 0.1-0.3, and water: 0.7-0.9, and
Service temperature 20-40 ℃ of handling of hydrofluoric acid solution, the time is 0.5-15 minute;
D. water cleans again, its remained on surface medicament of flush away;
E. after the calcium carbonate aqueous solution processing;
Like this, can finish the surface treatment of magnesium alloy.
8, as claim 1 or 4 or 7 described surface treatment method of Mg alloy, it is applied to the AZ91D magnesium alloy, and consisting of of described AZ91D magnesium alloy comprises: Al, Zn, Mn, Si, Cu, Fe, Ni and Mg.
9, as claim 1 or 4 or 7 described surface treatment method of Mg alloy, it is applied to β phase and the removal mutually of rich aluminium in the magnesium alloy.
10, as claim 1 or 4 or 7 described surface treatment method of Mg alloy, wherein, the operating time that calcium carbonate aqueous solution is handled is 30 to 60 minutes.
11, as claim 1 or 4 or 7 described surface treatment method of Mg alloy, wherein, the volumetric ratio of hydrofluoric acid, sulfuric acid and water is respectively hydrofluoric acid in described hydrofluoric acid and the vitriolic mixing solutions: 0.174, and sulfuric acid: 0.052, water: 0.774; Service temperature: 25 ℃; Operating time: 3.5 minutes.
12, as claim 1 or 4 or 7 described surface treatment method of Mg alloy, wherein, the volumetric ratio of hydrofluoric acid and water is respectively hydrofluoric acid in the solution of described hydrofluoric acid: 0.2, and water: 0.8; Service temperature: 25 ℃; Operating time: 3 minutes.
13, as claim 1 or 4 or 7 described surface treatment method of Mg alloy, wherein, the ratio of lime carbonate and water is 5wt% in the described calcium carbonate aqueous solution; Service temperature: 40 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230177A (en) * | 2011-04-25 | 2011-11-02 | 天津东义镁制品股份有限公司 | Magnesium alloy stripping solution and its stripping method |
| CN111139481A (en) * | 2020-01-15 | 2020-05-12 | 同济大学 | Stainless steel corrosive agent for fuel cell bipolar plate and metallographic phase preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3828446B2 (en) * | 2002-03-26 | 2006-10-04 | 日本ペイント株式会社 | Magnesium alloy surface cleaning method |
| CN1450200A (en) * | 2003-04-28 | 2003-10-22 | 中国第一汽车集团公司 | Brightening etchant for magnesium alloy |
| CN1242096C (en) * | 2003-04-29 | 2006-02-15 | 中国科学院金属研究所 | Method for preparing corrosion-proof wear-resistant nickel plating coat on the surface of magnesium and its alloy parts |
| CN1556247A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Solution foumula of magnesium, aluminium alloy weak acid activation technology |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230177A (en) * | 2011-04-25 | 2011-11-02 | 天津东义镁制品股份有限公司 | Magnesium alloy stripping solution and its stripping method |
| CN102230177B (en) * | 2011-04-25 | 2013-06-12 | 天津东义镁制品股份有限公司 | Magnesium alloy stripping solution and its stripping method |
| CN111139481A (en) * | 2020-01-15 | 2020-05-12 | 同济大学 | Stainless steel corrosive agent for fuel cell bipolar plate and metallographic phase preparation method |
| CN111139481B (en) * | 2020-01-15 | 2021-05-11 | 同济大学 | Stainless steel corrosive agent for fuel cell bipolar plate and metallographic phase preparation method |
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