CN105568339B - It is a kind of using magnesium/magnesium alloy as the multicoat composite material and preparation method of matrix - Google Patents

It is a kind of using magnesium/magnesium alloy as the multicoat composite material and preparation method of matrix Download PDF

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CN105568339B
CN105568339B CN201510968984.7A CN201510968984A CN105568339B CN 105568339 B CN105568339 B CN 105568339B CN 201510968984 A CN201510968984 A CN 201510968984A CN 105568339 B CN105568339 B CN 105568339B
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magnesium
magnesium alloy
arc oxidation
differential arc
coating
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CN105568339A (en
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崔蓝月
曾荣昌
李硕琦
张芬
靳涛
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Shandong University of Science and Technology
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon

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Abstract

The invention discloses a kind of using magnesium/magnesium alloy as the multicoat composite material and preparation method of matrix, which includes magnesium/magnesium alloy matrix, the differential arc oxidation coating being formed on magnesium/magnesium alloy matrix and the zinc stearate coating being formed on differential arc oxidation coating；The differential arc oxidation coating with a thickness of 3.9-4.7 μm；Zinc stearate coating with a thickness of 15.1-16.3 μm.Preparation method includes pretreatment, three steps of electro-deposition of differential arc oxidation and zinc stearate coating, its preparation process easily-controllable, high yield rate easy to operate, the thickness of each composite layer is easily controllable, and prepared composite material has the characteristics that super-hydrophobic, corrosion resistance is excellent.

Description

It is a kind of using magnesium/magnesium alloy as the multicoat composite material and preparation method of matrix
Technical field
The present invention relates to a kind of composite coating materials and preparation method thereof, more particularly to one kind is using magnesium/magnesium alloy as matrix The modified differential arc oxidation composite coating material and preparation method thereof of electro-deposition.
Background technique
Magnesium alloy is used for industrial application, such as automobile, electronics, aerospace, national defence as emerging structural metallic materials The fields such as military project, metallurgy, chemical, traffic have important application value and wide application prospect.It is good derived from its Machinability, hot formability energy, heating conduction, vibration absorbing performance and damping capacity etc..But, due to magnesium chemical property itself Vivaciously, standard electrode potential is very low, so that magnesium alloy is highly prone to corrode, so as to cause a series of problems.Therefore, magnesium or When Magnesium Alloy Industry materials'use, preservative treatment is firstly the need of one of the technical issues of solution.
In the prior art, there are three types of the approach for improving corrosion stability of magnesium alloy: alloying, working process and surface are modified. Wherein, by the improvement of manufacturing process, the corrosion resistance of magnesium alloy can also obtain certain promotion, such as by using isometrical angle Extruding, superplasticforming, quickly the advanced materials technology of preparing such as solidification, powder metallurgic method, the corrosion resistance of magnesium alloy have compared with Good improvement.But due to the chemical property that magnesium alloy is very active, magnesium conjunction can not be thoroughly solved only by processing technology is improved The corrosion-resistant problem of gold.
In recent years, modified become in surface uses technical way the most universal in the prior art.It is abundant in order to reach Protective value, super-hydrophobic coat favors by everybody.Moreover, magnesium alloy is as a kind of structural metallic materials, it is accordingly required in particular to from The new coating of the approach of coating structure and function integration design excellent corrosion-proof performance.So far, people have developed A variety of surface modified coats and process for modifying surface, and have developed numerous products.However, warp manufactured by the prior art The modified magnesium-alloy material in surface is crossed, there is all various deficiencies, be mainly manifested in such as corrosion resistance, binding force, durability Equal integrated performance indexs still have deficiency, and practical effect is not especially desirable.The surface modifying method of other magnesium alloys, Such as chemical composition coating, ion implanting, vapor deposition, polymer coating etc., generally existing corrosion resistance increase rate are little, resistance to Grind the disadvantages of durability is poor or problem.
Summary of the invention
Based on above-mentioned technical problem, the present invention provide it is a kind of using magnesium/magnesium alloy as the multicoat composite material of matrix, and The preparation method of the composite material.
The adopted technical solution is that:
It is a kind of using magnesium/magnesium alloy as the multicoat composite material of matrix, including magnesium/magnesium alloy matrix, be formed in magnesium/magnesium and close Differential arc oxidation coating on auri body and the zinc stearate coating being formed on differential arc oxidation coating；The differential arc oxidation applies Layer with a thickness of 3.9-4.7 μm；Zinc stearate coating with a thickness of 15.1-16.3 μm.
Above-mentioned zinc stearate coating is super-hydrophobic coat.
Preferably, above-mentioned by the multicoat composite material of matrix of magnesium/magnesium alloy is lamellar structure.
The differential arc oxidation composite coating material modified as the electro-deposition of matrix using magnesium/magnesium alloy of above structure form, Composite coating structure is fine and close and adhesive force is strong, has superior corrosion resisting property and longer service life.
It is above-mentioned using magnesium/magnesium alloy as the preparation method of the multicoat composite material of matrix, comprising the following steps:
A pre-treatment step: being polishing to surface without obvious scratch for magnesium/magnesium alloy blank, then with organic solvent and/or goes Ionized water cleans up, and is done with wind spare；
B differential arc oxidation step: at room temperature, pretreated using the mixed solution of phytic acid and sodium hydroxide as electrolyte Magnesium/magnesium alloy blank is as anode, and magnesium bar is as cathode, building two electrode systems of closure；The concentration of phytic acid is in mixed solution 8g/L, the concentration of sodium hydroxide are 10g/L；
Differential arc oxidation is divided into four-stage:
First is that the anodic oxidation stage: the voltage of two electrode systems of closure controls between 100-120V, and the time controls in 3- 4s；
Second is that the spark discharge stage: voltage slowly being increased, until adjusting between 240-260V, voltage adjustment time control System is in 10-12min；
Third is that the differential arc oxidation stage: voltage is maintained between 240-260V, and the time controls in 3-5min；
Fourth is that the blow-out stage: voltage is maintained between 240-260V, until spark finally disappears, explosion stops；
After the completion of differential arc oxidation, it is formed with differential arc oxidation coating on magnesium/magnesium alloy, takes out, rinsed, used with deionized water Wind is dry；It is placed in baking oven, at 80-120 DEG C, freeze-day with constant temperature handles 2-3h；
C zinc stearate electrodeposition step: at room temperature, using zinc stearate solution as electrolyte, magnesium/magnesium after differential arc oxidation is closed Gold is used as cathode, and platinum electrode is as anode, building two electrode systems of closure；Zinc stearate solution is by 1L organic solvent First addition 0.1mol stearic acid adds 0.05mol zinc nitrate and is formulated；
Adjusting voltage is 25V, and sedimentation time is controlled after the completion of 50-70min, deposition, formed on differential arc oxidation coating There is zinc stearate coating, take out, is rinsed with deionized water, is dry with wind；It is placed in baking oven, at 80-120 DEG C, freeze-day with constant temperature Handle 2-3h to get.
The direct bring of the above method has the technical effect that, under certain current density, the formation speed of oxidation film is higher than The micro-arc oxidation films of solution rate, formation have good binding force, intensity, corrosion resistance and certain self-reparing capability；Pass through The zinc stearate coating of electro-deposition preparation can realize the good combination with internal layer differential arc oxidation coating by the effect of electric current, and The ultra-hydrophobicity of itself effectively obstructs all kinds of ions in external environment and hydrone and passes through differential arc oxidation coating Pore corrosion magnesium/magnesium alloy.
That is, in above-mentioned technical proposal, by with good binding force, intensity, corrosion resistance and certain self-reparing capability Differential arc oxidation coating as transition zone；Then on the basis of transition zone, then one layer of electro-deposition super-hydrophobic zinc stearate coating, Obtain the differential arc oxidation composite coating material modified as the electro-deposition of matrix using magnesium/magnesium alloy.It is compound that this is effectively guaranteed this The compactness of coating and good corrosion resistance.
In addition, assembling sedimentation time control every time is 50-70min in the above method, primary concern is that, magnesium alloy mistake Micro- galvanic corrosion on surface will occur in electro-deposition system for a long time, the time is too short, and the zinc stearate coating deposited exists Surface is unevenly distributed；The deposition voltage of electro-deposition is limited to 25V, is because magnesium alloy deposition voltage is excessively high, i.e. current density Excessive to lead to the cracked or lifted off of its zinc stearate coating, current density is too small, and it is too thin and uneven to will lead to thicknesses of layers.
The core technology thought of above-mentioned technical proposal is: using electro-deposition techniques, realization will be with superhydrophobic characteristic Zinc stearate and differential arc oxidation coating are combined closely, to effectively close the differential of the arc using the superhydrophobic characteristic of zinc stearate coating The micropore of oxide covering.Thus, this surface modifying method, on the one hand, technically simpler, convenient and efficient, easily controllable； And at low cost, environment friendly and pollution-free, high yield rate.On the other hand, prepared modified by the electro-deposition of matrix of magnesium/magnesium alloy Differential arc oxidation composite coating material its is super-hydrophobic, corrosion resistance is excellent.
In addition, the preparation of zinc stearate super-hydrophobic coat can provide it is a kind of low cost, dynamical raising magnesium alloy it is resistance to The surface modifying method of corrosion.
Preferably, the polishing of above-mentioned magnesium/magnesium alloy blank is first to be roughly ground using grinding wheel or coarse sandpaper, then use 1500 Purpose carborundum paper is finely polished.
The direct bring of the optimal technical scheme has the technical effect that, easy to operate, and the good finish of matrix surface with Roughness is conducive to micro-arc oxidation process and preferably forms a film, to guarantee the uniformity and compactness of film forming.
In step c: zinc stearate solution is added by the way that 0.1mol stearic acid is first added in 1L organic solvent 0.05mol zinc nitrate is formulated；Preferably, the organic solvent is ethyl alcohol or acetone.
The direct bring of the technical solution has the technical effect that, the state of zinc ion, Ke Yiyou are presented in the zinc nitrate short time Effect is deposited on the sample surfaces for doing cathode.With the progress of reaction process, zinc nitrate further reacts with stearic acid shape At super-hydrophobic zinc stearate coating.
In conclusion the present invention compared with the existing technology, has the advantages that
1, the differential arc oxidation composite coating material modified as the electro-deposition of matrix using magnesium/magnesium alloy that the present invention prepares, Its filming performance is good, structure is uniform, and corrosion resistance is excellent, and has good super-hydrophobic effect.
2, preparation process of the present invention is simple, easily-controllable, high yield rate, short preparation period, and manufacturing cost is low.
Detailed description of the invention
Fig. 1 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the stereoscan photograph of coating (amplification factor is 20000 times)；
Fig. 2 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the contact angle figure of coating；
Fig. 3 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the comparison dynamic potential polarization curve figure of coating and not coated piece of magnesium alloy Mg-4Li-1Ca substrate；
Fig. 4-1 is the differential arc oxidation being modified using magnesium alloy Mg-4Li-1Ca as the electro-deposition of matrix obtained by embodiment 1 The impedance curve of composite coating；
Fig. 4-2 is the impedance curve of not coated piece of magnesium alloy Mg-4Li-1Ca substrate；
Fig. 5 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Liberation of hydrogen rate curve is impregnated in the comparison for closing coating and not coated piece of magnesium alloy Mg-4Li-1Ca substrate.
Fig. 6 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the profile scanning electromicroscopic photograph of coating (amplification factor is 5000 times).
Specific embodiment
The present invention provides a kind of using magnesium/magnesium alloy as the multicoat composite material of matrix, is laminar structured, including It magnesium/magnesium alloy matrix, the differential arc oxidation coating being formed on magnesium/magnesium alloy matrix and is formed on differential arc oxidation coating Zinc stearate coating；The differential arc oxidation coating with a thickness of 3.9-4.7 μm；Zinc stearate coating with a thickness of 15.1-16.3 μ m.Zinc stearate coating is super-hydrophobic coat.
Preparation method of the invention is described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
Basic material is magnesium alloy Mg-4Li-1Ca, the preparation method is as follows:
A pre-treatment step: being polishing to surface without obvious scratch for magnesium alloy Mg-4Li-1Ca blank, then with there is deionization Water cleans up, and is done with wind spare.Specific bruting process is first to be roughly ground using grinding wheel or coarse sandpaper, then use 1500 mesh Carborundum paper finely polished.
B differential arc oxidation step: at room temperature, pretreated using the mixed solution of phytic acid and sodium hydroxide as electrolyte Magnesium/magnesium alloy blank is as anode, and magnesium bar is as cathode, building two electrode systems of closure.The concentration of phytic acid is in mixed solution 8g/L, the concentration of sodium hydroxide are 10g/L.The specific preparation method of mixed solution are as follows: 8g phytic acid is first added in 1L distilled water, Add 10g sodium hydroxide to get.
Differential arc oxidation is divided into four-stage:
First is that the anodic oxidation stage: in 100V, the time is controlled in 3s for the voltage control of two electrode systems of closure；
Second is that the spark discharge stage: voltage slowly being increased, arrives 260V until adjusting, voltage adjustment time is controlled in 10- 12min；
Third is that differential arc oxidation and blow-out stage: voltage is maintained at 260V, until spark finally disappears, explosion stops.
After the completion of differential arc oxidation, it is formed with differential arc oxidation coating on magnesium/magnesium alloy, takes out, rinsed, used with deionized water Wind is dry；It is placed in baking oven, at 120 DEG C, freeze-day with constant temperature handles 3h.
C zinc stearate electrodeposition step: at room temperature, using zinc stearate solution as electrolyte, magnesium/magnesium after differential arc oxidation is closed Gold is used as cathode, and platinum electrode is as anode, building two electrode systems of closure；Zinc stearate solution is by first adding in 1L ethyl alcohol Enter 0.1mol stearic acid and add 0.05mol zinc nitrate to be formulated.
Adjusting voltage is 25V, and sedimentation time controls after the completion of 50min, deposition, is formed on differential arc oxidation coating hard Resin acid spelter coating takes out, and is rinsed with deionized water, is dry with wind；It is placed in baking oven, at 120 DEG C, freeze-day with constant temperature handles 2h, To obtain the final product.
Embodiment 2
Basic material is magnesium alloy AZ31, remaining is the same as embodiment 1.
Embodiment 3
Basic material is magnesium, remaining is the same as embodiment 1.
Embodiment 4
Basic material is Mg-1Li-Ca alloy, remaining is the same as embodiment 1.
Embodiment 5
Basic material is magnesium alloy Mg-4Li-1Ca, the preparation method is as follows:
A pre-treatment step: being polishing to surface without obvious scratch for magnesium alloy Mg-4Li-1Ca blank, then with there is deionization Water cleans up, and is done with wind spare.Specific bruting process is first to be roughly ground using grinding wheel or coarse sandpaper, then use 1500 mesh Carborundum paper finely polished.
B differential arc oxidation step: at room temperature, pretreated using the mixed solution of phytic acid and sodium hydroxide as electrolyte Magnesium/magnesium alloy blank is as anode, and magnesium bar is as cathode, building two electrode systems of closure.The concentration of phytic acid is in mixed solution 8g/L, the concentration of sodium hydroxide are 10g/L.The specific preparation method of mixed solution are as follows: 8g phytic acid is first added in 1L distilled water, Add 10g sodium hydroxide to get.
Differential arc oxidation is divided into four-stage:
First is that the anodic oxidation stage: in 120V, the time is controlled in 4s for the voltage control of two electrode systems of closure；
Second is that the spark discharge stage: voltage slowly being increased, arrives 240V until adjusting, voltage adjustment time is controlled in 10- 12min；
Third is that differential arc oxidation and blow-out stage: voltage is maintained at 240V, until spark finally disappears, explosion stops.
After the completion of differential arc oxidation, it is formed with differential arc oxidation coating on magnesium/magnesium alloy, takes out, rinsed, used with deionized water Wind is dry；It is placed in baking oven, at 100 DEG C, freeze-day with constant temperature handles 3h.
C zinc stearate electrodeposition step: at room temperature, using zinc stearate solution as electrolyte, magnesium/magnesium after differential arc oxidation is closed Gold is used as cathode, and platinum electrode is as anode, building two electrode systems of closure；Zinc stearate solution is by first adding in 1L ethyl alcohol Enter 0.1mol stearic acid and add 0.05mol zinc nitrate to be formulated.
Adjusting voltage is 25V, and sedimentation time controls after the completion of 70min, deposition, is formed on differential arc oxidation coating hard Resin acid spelter coating takes out, and is rinsed with deionized water, is dry with wind；It is placed in baking oven, at 100 DEG C, freeze-day with constant temperature handles 2h, To obtain the final product.
Embodiment 6
Basic material is magnesium alloy Mg-4Li-1Ca, the preparation method is as follows:
A pre-treatment step: being polishing to surface without obvious scratch for magnesium alloy Mg-4Li-1Ca blank, then with there is deionization Water cleans up, and is done with wind spare.Specific bruting process is first to be roughly ground using grinding wheel or coarse sandpaper, then use 1500 mesh Carborundum paper finely polished.
B differential arc oxidation step: at room temperature, pretreated using the mixed solution of phytic acid and sodium hydroxide as electrolyte Magnesium/magnesium alloy blank is as anode, and magnesium bar is as cathode, building two electrode systems of closure.The concentration of phytic acid is in mixed solution 8g/L, the concentration of sodium hydroxide are 10g/L.The specific preparation method of mixed solution are as follows: 8g phytic acid is first added in 1L distilled water, Add 10g sodium hydroxide to get.
Differential arc oxidation is divided into four-stage:
First is that the anodic oxidation stage: in 110V, the time is controlled in 4s for the voltage control of two electrode systems of closure；
Second is that the spark discharge stage: voltage slowly being increased, arrives 250V until adjusting, voltage adjustment time is controlled in 10- 12min；
Third is that differential arc oxidation and blow-out stage: voltage is maintained at 250V, until spark finally disappears, explosion stops.
After the completion of differential arc oxidation, it is formed with differential arc oxidation coating on magnesium/magnesium alloy, takes out, rinsed, used with deionized water Wind is dry；It is placed in baking oven, at 80 DEG C, freeze-day with constant temperature handles 3h.
C zinc stearate electrodeposition step: at room temperature, using zinc stearate solution as electrolyte, magnesium/magnesium after differential arc oxidation is closed Gold is used as cathode, and platinum electrode is as anode, building two electrode systems of closure；Zinc stearate solution is by first adding in 1L ethyl alcohol Enter 0.1mol stearic acid and add 0.05mol zinc nitrate to be formulated.
Adjusting voltage is 25V, and sedimentation time controls after the completion of 60min, deposition, is formed on differential arc oxidation coating hard Resin acid spelter coating takes out, and is rinsed with deionized water, is dry with wind；It is placed in baking oven, at 100 DEG C, freeze-day with constant temperature handles 2h, To obtain the final product.
Embodiment 7
Basic material is magnesium alloy Mg-4Li-1Ca, the preparation method is as follows:
A pre-treatment step: being polishing to surface without obvious scratch for magnesium alloy Mg-4Li-1Ca blank, then with there is deionization Water cleans up, and is done with wind spare.Specific bruting process is first to be roughly ground using grinding wheel or coarse sandpaper, then use 1500 mesh Carborundum paper finely polished.
B differential arc oxidation step: at room temperature, pretreated using the mixed solution of phytic acid and sodium hydroxide as electrolyte Magnesium/magnesium alloy blank is as anode, and magnesium bar is as cathode, building two electrode systems of closure.The concentration of phytic acid is in mixed solution 8g/L, the concentration of sodium hydroxide are 10g/L.The specific preparation method of mixed solution are as follows: 8g phytic acid is first added in 1L distilled water, Add 10g sodium hydroxide to get.
Differential arc oxidation is divided into four-stage:
First is that the anodic oxidation stage: in 105V, the time is controlled in 3s for the voltage control of two electrode systems of closure；
Second is that the spark discharge stage: voltage slowly being increased, arrives 260V until adjusting, voltage adjustment time is controlled in 10- 12min；
Third is that differential arc oxidation and blow-out stage: voltage is maintained at 260V, until spark finally disappears, explosion stops.
After the completion of differential arc oxidation, it is formed with differential arc oxidation coating on magnesium/magnesium alloy, takes out, rinsed, used with deionized water Wind is dry；It is placed in baking oven, at 100 DEG C, freeze-day with constant temperature handles 3h.
C zinc stearate electrodeposition step: at room temperature, using zinc stearate solution as electrolyte, magnesium/magnesium after differential arc oxidation is closed Gold is used as cathode, and platinum electrode is as anode, building two electrode systems of closure；Zinc stearate solution is by first adding in 1L ethyl alcohol Enter 0.1mol stearic acid and add 0.05mol zinc nitrate to be formulated.
Adjusting voltage is 25V, and sedimentation time controls after the completion of 65min, deposition, is formed on differential arc oxidation coating hard Resin acid spelter coating takes out, and is rinsed with deionized water, is dry with wind；It is placed in baking oven, at 80 DEG C, freeze-day with constant temperature handles 3h, i.e., ?.
Selection example 1 individually or with not coated piece of magnesium alloy substrates is scanned electricity as embodiment is represented Amplify 20000 times of observations, contact angle, electro-chemical test analysis, the immersion 85h progress liberation of hydrogen test point of 3.5%NaCl solution under mirror Analysis or comparative analysis, as a result as shown in Figures 1 to 6.
Fig. 1 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the stereoscan photograph of coating (amplification factor is 20000 times).As shown in Figure 1, it can be seen that uniform lamella is presented in coating It shape structure and uniformly sprawls.
Fig. 2 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the contact angle figure of coating.As shown in Fig. 2, zinc stearate coating contact angle is 153.5 °, super-hydrophobic coat is shown as.
Fig. 3 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the comparison dynamic potential polarization curve figure of coating and not coated piece of magnesium alloy Mg-4Li-1Ca substrate.
As shown in figure 3, comparing result can be seen that using magnesium alloy as the multicoat composite material of matrix with it is not coated piece of Magnesium alloy compares, and corrosion current density is substantially reduced (by 3.55 × 10-5A/cm2It is reduced to 7.68 × 10-8A/cm2)。 The result shows that surface covers the modified differential arc oxidation composite coating of electro-deposition relative to uncoated magnesium alloy Mg-4Li-1Ca Magnesium alloy possess excellent corrosion resistance.
Fig. 4-1 is the differential arc oxidation being modified using magnesium alloy Mg-4Li-1Ca as the electro-deposition of matrix obtained by embodiment 1 The impedance curve of composite coating；Fig. 4-2 is the impedance curve of not coated piece of magnesium alloy Mg-4Li-1Ca substrate.Such as Fig. 4-1 and Shown in Fig. 4-2, comparing result can be seen that compound using the magnesium alloy Mg-4Li-1Ca differential arc oxidation modified as the electro-deposition of matrix Compared with not coated piece of magnesium alloy Mg-4Li-1Ca, AC impedance arc significantly increases coating.The result shows that relative to not plating The magnesium alloy Mg-4Li-1Ca of film, the magnesium alloy of the modified differential arc oxidation composite coating of surface covering electro-deposition possess excellent resist Corrosive nature.
Fig. 5 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Liberation of hydrogen rate curve is impregnated in the comparison for closing coating and not coated piece of magnesium alloy Mg-4Li-1Ca.As shown in figure 5, comparing result can It is closed using finding out using the magnesium alloy Mg-4Li-1Ca differential arc oxidation composite coating modified as the electro-deposition of matrix and not coated piece of magnesium Golden Mg-4Li-1Ca compares, heavy by the electricity of matrix of magnesium alloy Mg-4Li-1Ca after impregnating 85h in 3.5%NaCl solution The modified differential arc oxidation composite coating liberation of hydrogen rate of product significantly reduces (liberation of hydrogen rate is bordering on 0).
Fig. 6 is multiple using differential arc oxidation magnesium alloy Mg-4Li-1Ca modified as the electro-deposition of matrix obtained by embodiment 1 Close the profile scanning electromicroscopic photograph of coating (amplification factor is 5000 times).As shown in fig. 6, the strip portion to become clear in figure is the differential of the arc The thickness of oxide covering, the brighter strip portion in top is the thickness of zinc stearate coating, it can be seen from the figure that differential arc oxidation Coating with a thickness of 3.9-4.7 μm, zinc stearate coating with a thickness of 15.1-16.3 μm, the overall thickness of above-mentioned coating is 19-21 μm。
Respectively to embodiment 2-4 be scanned under Electronic Speculum amplify 20000 times of observations, contact angle, electro-chemical test analyze, Liberation of hydrogen analysis of experiments is carried out after impregnating 85h in 3.5%NaCl solution, acquired results detection is basic with the testing result of embodiment 1 It coincide.Illustrate that basic material of the invention can both select magnesium, all kinds of magnesium alloys can also be selected.

Claims (3)

1. a kind of using magnesium/magnesium alloy as the preparation method of the multicoat composite material of matrix, it is characterised in that the following steps are included:
A pre-treatment step: magnesium/magnesium alloy blank is polishing to surface without obvious scratch, then uses organic solvent and/or deionization Water cleans up, and is done with wind spare；
B differential arc oxidation step: at room temperature, using the mixed solution of phytic acid and sodium hydroxide as electrolyte, pretreated magnesium/magnesium Alloy blank is as anode, and magnesium bar is as cathode, building two electrode systems of closure；The concentration of phytic acid is 8g/L in mixed solution, The concentration of sodium hydroxide is 10g/L；
Differential arc oxidation is divided into four-stage:
First is that the anodic oxidation stage: the voltage of two electrode systems of closure controls between 100-120V, and the time controls in 3-4s；
Second is that the spark discharge stage: voltage slowly being increased, until adjusting between 240-260V, voltage adjustment time control exists 10-12min；
Third is that the differential arc oxidation stage: voltage is maintained between 240-260V, and the time controls in 3-5min；
Fourth is that the blow-out stage: voltage is maintained between 240-260V, until spark finally disappears, explosion stops；
After the completion of differential arc oxidation, it is formed with differential arc oxidation coating on magnesium/magnesium alloy, takes out, rinsed with deionized water, use wind It is dry；It is placed in baking oven, at 80-120 DEG C, freeze-day with constant temperature handles 2-3h；
C zinc stearate electrodeposition step: at room temperature, using zinc stearate solution as electrolyte, the magnesium/magnesium alloy after differential arc oxidation is made For cathode, platinum electrode is as anode, building two electrode systems of closure；Zinc stearate solution is by first adding in 1L organic solvent Enter 0.1mol stearic acid and add 0.05mol zinc nitrate to be formulated；
Adjusting voltage is 25V, and sedimentation time controls after the completion of 50-70min, deposition, is formed on differential arc oxidation coating hard Resin acid spelter coating takes out, and is rinsed with deionized water, is dry with wind；It is placed in baking oven, at 80-120 DEG C, freeze-day with constant temperature processing 2-3h to get.
2. it is according to claim 1 a kind of using magnesium/magnesium alloy as the preparation method of the multicoat composite material of matrix, it is special Sign is, in step a: the polishing of the magnesium/magnesium alloy blank is first to be roughly ground using grinding wheel or coarse sandpaper, then use 1500 Purpose carborundum paper is finely polished.
3. it is according to claim 1 a kind of using magnesium/magnesium alloy as the preparation method of the multicoat composite material of matrix, it is special Sign is, in step c: the organic solvent is ethyl alcohol or acetone.
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