CN104878377A - Method for preparing graphene oxide and micro-arc oxidized ceramic composite coating on surface of magnesium alloy - Google Patents
Method for preparing graphene oxide and micro-arc oxidized ceramic composite coating on surface of magnesium alloy Download PDFInfo
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Abstract
The invention provides a method for preparing a graphene oxide and micro-arc oxidized ceramic composite coating on the surface of a magnesium alloy and relates to a method of preparing a coating on the surface of the magnesium alloy. The method is used for solving the problem of poor corrosion resistance of the micro-arc oxidized ceramic coating of a porous structure due to large contact area of the coating with a corrosive medium in the corrosion process. The method comprises the following steps: 1, magnesium alloy pre-processing; 2, ultrasonic processing; 3, oil removal; 4, micro-arc oxidization; 5, graphene oxide preparation; 6, application of the graphene oxide solution to the micro-arc oxidized ceramic coating on the magnesium alloy, thereby obtaining the magnesium alloy coated with the graphene oxide and micro-arc oxidized ceramic composite coating. According to the method, the corrosion current density of the graphene oxide and micro-arc oxidized ceramic composite coating is reduced to 14.5nA/cm<2>, which is 1/7240 of the corrosion current of the matrix magnesium alloy. The invention relates to the method for preparing the graphene oxide and micro-arc oxidized ceramic composite coating on the surface of the magnesium alloy.
Description
Technical field
The present invention relates to a kind of method preparing rete at Mg alloy surface.
Background technology
Graphene (graphene) is a kind of New Two Dimensional nano material be found for 2004.The unique electronic that Graphene shows and physical property, have important application prospect in fields such as molectronics, micro-nano device, matrix material, field emmision material, sensor, battery and hydrogen storage materials.With it Graphene, people see the more how practical possibility of carbon nanomaterial, although so Graphene be found to decades until now, but it has evoked scientists and has studied interest greatly, become rapidly the study hotspot in the field such as Materials science and Condensed Matter Physics, there is important theoretical and experimental study be worth, be expected to start the technological revolution of a new carbon nanomaterial in 21 century.
Research shows to peel off the graphene oxide (GO) of preparation containing a large amount of oxygen-content active groups by graphite oxide, comprise carboxyl, carbonyl, hydroxyl and epoxy group(ing) etc., epoxy group(ing) and hydroxyl are mainly positioned on the basal plane of graphene oxide, and carboxyl and carbonyl are then distributed in the edge of graphene oxide usually.So be very easily dissolved in the water, form the colloidal solution of graphene oxide, aqueous environment is that the carboxyl of graphene oxide and hydroxyl provide abundant hydrogen ion, along with the evaporation of moisture, graphene oxide lamella is due to the effect of hydrogen bond, and self-assembly forms the neat graphene oxide film of structure.This membrane structure is stablized, and can stand the corrosion of soda acid and have stronger opacity, effectively can stop the erosion of corrosive medium, greatly improves corrosion resistance of magnesium alloy energy.
Differential arc oxidization technique (Microarc oxidation, MAO) also known as micro-plasma oxidation (Micro-plasma oxidation, MPO), it is a kind of new technology at metallic surface growth in situ ceramic membrane, at the TRANSIENT HIGH TEMPERATURE High Pressure that aluminium, magnesium, titanium and titanium alloys surface rely on arc discharge to produce, directly matrix metal oxidation and sinter can be become membrane of oxide ceramics, material is not introduced from outside, be different from general process for modifying surface, make the high-performance of the existing ceramic membrane of micro-arc oxidation films, maintain again the bonding force of oxide film and matrix.Differential arc oxidation film layer compact structure, toughness is high, has good wear-resisting, corrosion-resistant, the characteristic such as high temperature impact resistance and electrical isolation.
This technology has the feature with being easy to realize rete function point analysis simple to operate, and differential arc oxidization technique is simpler than the technique of the technology such as plasma spraying, laser melting coating, convenient operation, does not cause environmental pollution, is a brand-new environmental type surface treatment technology of material; Its rete is than the oxide film even compact of anodizing technology gained, and comprehensive mechanical performance is high.Differential arc oxidation film layer has possessed the advantage of anode oxide film and ceramic film, has wide practical use in many fields such as military project, aerospace, machinery, weaving, automobile, medical treatment, electronics, decorations.
But; in micro-arc oxidation process condition; faraday region operating voltage be oxidized by common anode is incorporated into electrion region; this makes to deposit a large amount of discharge channels in ceramic film more, just because of this, and this special vesicular structure; this makes ceramic film in corrosion process; there is larger contact area with corrosive medium, for a long time effectively can not provide protection mechanism, be unfavorable for the widespread use of magnesium alloy.Therefore, how effectively to set up Micro-Arc Oxidized Ceramic Coating sealing of hole mechanism, particularly important.
Summary of the invention
The object of the invention is to solve Micro-Arc Oxidized Ceramic Coating is vesicular structure, larger contact area is had with corrosive medium in corrosion process, cause the problem of corrosion-resistant, and a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface is provided.
Prepare a method for graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface, complete according to the following steps:
One, magnesium alloy pre-treatment: use 180#SiC sand paper, 1000#SiC sand paper and 2000#SiC sand paper to carry out grinding process to magnesium alloy successively, obtain the magnesium alloy of surface-brightening;
Two, supersound process: the magnesium alloy of surface-brightening is immersed in acetone, supersound process 3min ~ 10min under ultrasonic power is 200W ~ 300W, obtains the magnesium alloy after supersound process;
Three, oil removing: first the magnesium alloy after supersound process being immersed in temperature is 60 DEG C ~ 75 DEG C, and concentration is 10min ~ 20min in the NaOH solution of 40g/L ~ 50g/L, obtains the magnesium alloy after NaOH solution process; Magnesium alloy after NaOH solution process being immersed in temperature is 60 DEG C ~ 75 DEG C, and concentration is 10min ~ 20min in the sodium radio-phosphate,P-32 solution of 10g/L ~ 20g/L, obtains the magnesium alloy after sodium radio-phosphate,P-32 solution process; Use distilled water to rinse 3 times ~ 5 times to the magnesium alloy after sodium radio-phosphate,P-32 solution process, re-use hair dryer and dry up, obtain the magnesium alloy after oil removing;
Four, differential arc oxidation: the magnesium alloy after oil removing is placed in the stainless steel electrolytic groove that electrolytic solution is housed, the magnesium alloy after oil removing is connected with the positive pole of power supply, as anode, stainless electrolyzer is connected with the negative pole of power supply, as negative electrode; Adopting pulse mao power source to power, is 0.5A/dm in current density
2~ 0.8A/dm
2, dutycycle be 10% ~ 40% and supply frequency be differential arc oxidation 5min ~ 15min under 500Hz ~ 2000Hz, obtain surface containing the magnesium alloy of Micro-Arc Oxidized Ceramic Coating;
Electrolytic solution described in step 4 is made up of water glass, potassium hydroxide and Sodium Fluoride, and solvent is water; The concentration of described electrolytic solution mesosilicic acid sodium is 20g/L ~ 40g/L, and the concentration of potassium hydroxide is 3g/L ~ 8g/L, and the concentration of Sodium Fluoride is 1g/L ~ 5g/L;
Five, prepare graphene oxide: joined by natural graphite powder at 0 DEG C in the mixing acid of sulfuric acid and nitric acid, then low whipping speed is stir under 80r/min ~ 150r/min, and by KMnO
4dividing joins in the mixing acid of sulfuric acid and nitric acid 2 times ~ 5 times; Low whipping speed is 100r/min ~ 200r/min and temperature is again stirring reaction 2h ~ 3h at 35 DEG C ~ 40 DEG C, then adds distilled water, then low whipping speed is stirring reaction 2h ~ 3h under 100r/min ~ 200r/min, then adds the H that massfraction is 1.8% ~ 2%
2o
2solution, obtains reaction solution; By reaction solution supersound process 24h ~ 30h under ultrasonic power is 200W ~ 400W, obtain suspension liquid; Successively functional quality mark be 5% HCl solution and distilled water 3 times ~ 5 times are washed to suspension liquid, obtain graphene oxide;
The mixing acid of the sulfuric acid described in step 5 and nitric acid be by massfraction be 91.79% ~ 93.81% sulfuric acid and massfraction be 6.19% ~ 9.21% nitric acid be mixed with and form; Described massfraction be 91.79% ~ 93.81% sulfuric acid and massfraction be the volume ratio of the nitric acid of 6.19% ~ 9.21% be 150:(13 ~ 20);
The volume ratio of the mixing acid of the quality of the natural graphite powder described in step 5 and sulfuric acid and nitric acid is 5g:(120mL ~ 130mL);
Natural graphite powder described in step 5 and KMnO
4mass ratio be 1:3;
The mixing acid of the sulfuric acid described in step 5 and nitric acid and the volume ratio of distilled water are 1:(2 ~ 3);
The mixing acid of the sulfuric acid described in step 5 and nitric acid and massfraction are the H of 1.8% ~ 2%
2o
2the volume ratio of solution is 1:(7 ~ 9);
Six, graphene oxide is joined in distilled water, obtain the graphene oxide solution that concentration is 1mg/L; Be that the graphene oxide solution of 1mg/L is coated in the Micro-Arc Oxidized Ceramic Coating of the magnesium alloy of surface containing Micro-Arc Oxidized Ceramic Coating by concentration, apply 3 ~ 5 times, dry 1h ~ 2h at temperature is 40 DEG C ~ 50 DEG C, obtains the magnesium alloy that surface coverage has graphene oxide and arc differential oxide ceramic composite film again.
Advantage of the present invention:
One, the present invention utilizes self-assembling technique, graphene oxide suspension is dripped and is coated in magnesium alloy differential arc oxidation film layer surface, graphene oxide invades in ceramic film duct, original position forms graphene oxide composite film, reduces the porosity of ceramic film, and graphene oxide film Stability Analysis of Structures, the corrosion of soda acid can be stood, there is good opacity, effectively can stop the erosion of corrosive medium, significantly improve corrosion resistance of magnesium alloy energy;
Two, preparation technology of the present invention is simple, and cost value is cheap, is suitable for difform device; The present invention can significantly improve corrosion resistance of magnesium alloy energy;
Three, the matrix corrosion current density of ZK60 magnesium alloy is 0.105mA/cm
2, after differential arc oxidization technique process, Mg alloy surface forms layer of ceramic film layer, and its thickness is 10 μm ~ 20 μm, and Corrosion Behaviors of Magnesium Alloys electric current is reduced to 67.2nA/cm
2, corrosion current reduces nearly 4 orders of magnitude, and corrosion resistance of magnesium alloy can significantly improve; And after self-assembly of the present invention coating concentration is the graphene oxide solution 3 times of 1mg/L, ceramic film surface forms dense oxide Graphene rete, its thickness is only 4 ~ 6 μm, and the corrosion electric current density of graphene oxide and arc differential oxide ceramic composite film reduces most 14.5nA/cm
2, be 1/5 of Micro-Arc Oxidized Ceramic Coating corrosion current, be 1/7240 of matrix Corrosion Behaviors of Magnesium Alloys electric current, corrosion resistance nature improves further, and this also illustrates and uses method of the present invention can significantly improve corrosion resistance of magnesium alloy energy.
The present invention can obtain a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface.
Accompanying drawing explanation
Fig. 1 is the surperficial SEM figure that the magnesium alloy of Micro-Arc Oxidized Ceramic Coating is contained on surface that test one step 4 obtains;
Fig. 2 is the enlarged view of Fig. 1;
Fig. 3 is that the surface coverage that test one step 6 obtains has the surperficial SEM of the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film to scheme;
Fig. 4 is the enlarged view of Fig. 3;
Fig. 5 is the section S EM figure that the magnesium alloy of Micro-Arc Oxidized Ceramic Coating is contained on surface that test one step 4 obtains, and in Fig. 5,1 is magnesium alloy substrate, and 2 is differential arc oxidation film layer, and 3 is epoxy resin;
Fig. 6 is that the surface coverage that test one step 6 obtains has the section S EM of the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film to scheme, and in Fig. 6,1 is magnesium alloy substrate, and 2 is graphene oxide rete, and 3 is differential arc oxidation film layer, and 4 is epoxy resin;
Fig. 7 is dynamic potential polarization curve, and in Fig. 7,1 is the dynamic potential polarization curve of magnesium alloy, and 2 is the dynamic potential polarization curve of Micro-Arc Oxidized Ceramic Coating, and 3 is the dynamic potential polarization curve of graphene oxide and arc differential oxide ceramic composite film.
Embodiment
Embodiment one: present embodiment is that a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface completes according to the following steps:
Prepare a method for graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface, complete according to the following steps:
One, magnesium alloy pre-treatment: use 180#SiC sand paper, 1000#SiC sand paper and 2000#SiC sand paper to carry out grinding process to magnesium alloy successively, obtain the magnesium alloy of surface-brightening;
Two, supersound process: the magnesium alloy of surface-brightening is immersed in acetone, supersound process 3min ~ 10min under ultrasonic power is 200W ~ 300W, obtains the magnesium alloy after supersound process;
Three, oil removing: first the magnesium alloy after supersound process being immersed in temperature is 60 DEG C ~ 75 DEG C, and concentration is 10min ~ 20min in the NaOH solution of 40g/L ~ 50g/L, obtains the magnesium alloy after NaOH solution process; Magnesium alloy after NaOH solution process being immersed in temperature is 60 DEG C ~ 75 DEG C, and concentration is 10min ~ 20min in the sodium radio-phosphate,P-32 solution of 10g/L ~ 20g/L, obtains the magnesium alloy after sodium radio-phosphate,P-32 solution process; Use distilled water to rinse 3 times ~ 5 times to the magnesium alloy after sodium radio-phosphate,P-32 solution process, re-use hair dryer and dry up, obtain the magnesium alloy after oil removing;
Four, differential arc oxidation: the magnesium alloy after oil removing is placed in the stainless steel electrolytic groove that electrolytic solution is housed, the magnesium alloy after oil removing is connected with the positive pole of power supply, as anode, stainless electrolyzer is connected with the negative pole of power supply, as negative electrode; Adopting pulse mao power source to power, is 0.5A/dm in current density
2~ 0.8A/dm
2, dutycycle be 10% ~ 40% and supply frequency be differential arc oxidation 5min ~ 15min under 500Hz ~ 2000Hz, obtain surface containing the magnesium alloy of Micro-Arc Oxidized Ceramic Coating;
Electrolytic solution described in step 4 is made up of water glass, potassium hydroxide and Sodium Fluoride, and solvent is water; The concentration of described electrolytic solution mesosilicic acid sodium is 20g/L ~ 40g/L, and the concentration of potassium hydroxide is 3g/L ~ 8g/L, and the concentration of Sodium Fluoride is 1g/L ~ 5g/L;
Five, prepare graphene oxide: joined by natural graphite powder at 0 DEG C in the mixing acid of sulfuric acid and nitric acid, then low whipping speed is stir under 80r/min ~ 150r/min, and by KMnO
4dividing joins in the mixing acid of sulfuric acid and nitric acid 2 times ~ 5 times; Low whipping speed is 100r/min ~ 200r/min and temperature is again stirring reaction 2h ~ 3h at 35 DEG C ~ 40 DEG C, then adds distilled water, then low whipping speed is stirring reaction 2h ~ 3h under 100r/min ~ 200r/min, then adds the H that massfraction is 1.8% ~ 2%
2o
2solution, obtains reaction solution; By reaction solution supersound process 24h ~ 30h under ultrasonic power is 200W ~ 400W, obtain suspension liquid; Successively functional quality mark be 5% HCl solution and distilled water 3 times ~ 5 times are washed to suspension liquid, obtain graphene oxide;
The mixing acid of the sulfuric acid described in step 5 and nitric acid be by massfraction be 91.79% ~ 93.81% sulfuric acid and massfraction be 6.19% ~ 9.21% nitric acid be mixed with and form; Described massfraction be 91.79% ~ 93.81% sulfuric acid and massfraction be the volume ratio of the nitric acid of 6.19% ~ 9.21% be 150:(13 ~ 20);
The volume ratio of the mixing acid of the quality of the natural graphite powder described in step 5 and sulfuric acid and nitric acid is 5g:(120mL ~ 130mL);
Natural graphite powder described in step 5 and KMnO
4mass ratio be 1:3;
The mixing acid of the sulfuric acid described in step 5 and nitric acid and the volume ratio of distilled water are 1:(2 ~ 3);
The mixing acid of the sulfuric acid described in step 5 and nitric acid and massfraction are the H of 1.8% ~ 2%
2o
2the volume ratio of solution is 1:(7 ~ 9);
Six, graphene oxide is joined in distilled water, obtain the graphene oxide solution that concentration is 1mg/L; Be that the graphene oxide solution of 1mg/L is coated in the Micro-Arc Oxidized Ceramic Coating of the magnesium alloy of surface containing Micro-Arc Oxidized Ceramic Coating by concentration, apply 3 ~ 5 times, dry 1h ~ 2h at temperature is 40 DEG C ~ 50 DEG C, obtains the magnesium alloy that surface coverage has graphene oxide and arc differential oxide ceramic composite film again.
The advantage of present embodiment:
One, present embodiment utilizes self-assembling technique, graphene oxide suspension is dripped and is coated in magnesium alloy differential arc oxidation film layer surface, graphene oxide invades in ceramic film duct, original position forms graphene oxide composite film, reduces the porosity of ceramic film, and graphene oxide film Stability Analysis of Structures, the corrosion of soda acid can be stood, there is good opacity, effectively can stop the erosion of corrosive medium, significantly improve corrosion resistance of magnesium alloy energy;
Two, present embodiment preparation technology is simple, and cost value is cheap, is suitable for difform device; Present embodiment can significantly improve corrosion resistance of magnesium alloy energy;
Three, the matrix corrosion current density of ZK60 magnesium alloy is 0.105mA/cm
2, after differential arc oxidization technique process, Mg alloy surface forms layer of ceramic film layer, and its thickness is 10 μm ~ 20 μm, and Corrosion Behaviors of Magnesium Alloys electric current is reduced to 67.2nA/cm
2, corrosion current reduces nearly 4 orders of magnitude, and corrosion resistance of magnesium alloy can significantly improve; And after present embodiment self-assembly coating concentration is the graphene oxide solution 3 times of 1mg/L, ceramic film surface forms dense oxide Graphene rete, its thickness is only 4 ~ 6 μm, and the corrosion electric current density of graphene oxide and arc differential oxide ceramic composite film reduces most 14.5nA/cm
2, be 1/5 of Micro-Arc Oxidized Ceramic Coating corrosion current, be 1/7240 of matrix Corrosion Behaviors of Magnesium Alloys electric current, corrosion resistance nature improves further, and this also illustrates and uses the method for present embodiment can significantly improve corrosion resistance of magnesium alloy energy.
Present embodiment can obtain a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface.
Embodiment two: present embodiment and embodiment one difference are: the magnesium alloy described in step one is ZK60 magnesium alloy.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: the thickness being coated with graphene oxide rete in the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film described in step 6 is 4 μm ~ 6 μm.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: described in step 6 be coated with Micro-Arc Oxidized Ceramic Coating in the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film thickness be 13 μm ~ 20 μm.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: in step 4, the magnesium alloy after oil removing is placed in the stainless steel electrolytic groove that electrolytic solution is housed, magnesium alloy after oil removing is connected with the positive pole of power supply, as anode, stainless electrolyzer is connected with the negative pole of power supply, as negative electrode; Adopting pulse mao power source to power, is 0.6A/dm in current density
2~ 0.7A/dm
2, dutycycle be 10% ~ 40% and supply frequency be differential arc oxidation 5min ~ 10min under 1000Hz ~ 2000Hz, obtain surface containing the magnesium alloy of Micro-Arc Oxidized Ceramic Coating.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: the electrolytic solution described in step 4 is made up of water glass, potassium hydroxide and Sodium Fluoride, solvent is water; The concentration of described electrolytic solution mesosilicic acid sodium is 25g/L ~ 35g/L, and the concentration of potassium hydroxide is 4g/L ~ 6g/L, and the concentration of Sodium Fluoride is 2g/L ~ 4g/L.Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: the mixing acid of the sulfuric acid described in step 5 and nitric acid be by massfraction be 92% ~ 93% sulfuric acid and massfraction be 7% ~ 8% nitric acid be mixed with and form; Described massfraction be 92% ~ 93% sulfuric acid and massfraction be the volume ratio of the nitric acid of 7% ~ 8%% be 150:(13 ~ 18).Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: the volume ratio of the mixing acid of the quality of the natural graphite powder described in step 5 and sulfuric acid and nitric acid is 5g:(120mL ~ 125mL).Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: the mixing acid of the sulfuric acid described in step 5 and nitric acid and the volume ratio of distilled water are 1:(2 ~ 2.5).Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: the mixing acid of the sulfuric acid described in step 5 and nitric acid and massfraction are the H of 1.8% ~ 2%
2o
2the volume ratio of solution is 1:(7 ~ 8).Other steps are identical with embodiment one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface completes according to the following steps:
One, magnesium alloy pre-treatment: use 180#SiC sand paper, 1000#SiC sand paper and 2000#SiC sand paper to carry out grinding process to magnesium alloy successively, obtain the magnesium alloy of surface-brightening;
Two, supersound process: the magnesium alloy of surface-brightening is immersed in acetone, supersound process 8min under ultrasonic power is 300W, obtains the magnesium alloy after supersound process;
Three, oil removing: first the magnesium alloy after supersound process being immersed in temperature is 70 DEG C, and concentration is 15min in the NaOH solution of 45g/L, obtains the magnesium alloy after NaOH solution process; Magnesium alloy after NaOH solution process being immersed in temperature is 70 DEG C, and concentration is 15min in the sodium radio-phosphate,P-32 solution of 15g/L, obtains the magnesium alloy after sodium radio-phosphate,P-32 solution process; Use distilled water to rinse 4 times to the magnesium alloy after sodium radio-phosphate,P-32 solution process, re-use hair dryer and dry up, obtain the magnesium alloy after oil removing;
Four, differential arc oxidation: the magnesium alloy after oil removing is placed in the stainless steel electrolytic groove that electrolytic solution is housed, the magnesium alloy after oil removing is connected with the positive pole of power supply, as anode, stainless electrolyzer is connected with the negative pole of power supply, as negative electrode; Adopting pulse mao power source to power, is 0.6A/dm in current density
2, dutycycle be 30% and supply frequency be differential arc oxidation 10min under 1000Hz, obtain surface containing the magnesium alloy of Micro-Arc Oxidized Ceramic Coating;
Electrolytic solution described in step 4 is made up of water glass, potassium hydroxide and Sodium Fluoride, and solvent is water; The concentration of described electrolytic solution mesosilicic acid sodium is 30g/L, and the concentration of potassium hydroxide is 6g/L, and the concentration of Sodium Fluoride is 2g/L;
Five, prepare graphene oxide: joined by natural graphite powder at 0 DEG C in the mixing acid of sulfuric acid and nitric acid, then low whipping speed is stir under 100r/min, and by KMnO
4divide and join for 3 times in the mixing acid of sulfuric acid and nitric acid; Low whipping speed is 200r/min and temperature is again stirring reaction 3h at 40 DEG C, then adds distilled water, then low whipping speed is stirring reaction 2.5h under 200r/min, then adds the H that massfraction is 2%
2o
2solution, obtains reaction solution; By reaction solution supersound process 28h under ultrasonic power is 300W, obtain suspension liquid; Successively functional quality mark be 5% HCl solution and distilled water 4 times are washed to suspension liquid, obtain graphene oxide;
The mixing acid of the sulfuric acid described in step 5 and nitric acid be by massfraction be 93% sulfuric acid and massfraction be 8% nitric acid be mixed with and form; Described massfraction be 93% sulfuric acid and massfraction be the volume ratio of the nitric acid of 8% be 150:18;
The volume ratio of the mixing acid of the quality of the natural graphite powder described in step 5 and sulfuric acid and nitric acid is 5g:125mL;
Natural graphite powder described in step 5 and KMnO
4mass ratio be 1:3;
The mixing acid of the sulfuric acid described in step 5 and nitric acid and the volume ratio of distilled water are 1:2.5;
The mixing acid of the sulfuric acid described in step 5 and nitric acid and massfraction are the H of 2%
2o
2the volume ratio of solution is 1:8;
Six, graphene oxide is joined in distilled water, obtain the graphene oxide solution that concentration is 1mg/L; Be that the graphene oxide solution of 1mg/L is coated in the Micro-Arc Oxidized Ceramic Coating of the magnesium alloy of surface containing Micro-Arc Oxidized Ceramic Coating by concentration, apply 3 times, dry 2h at temperature is 45 DEG C, obtains the magnesium alloy that surface coverage has graphene oxide and arc differential oxide ceramic composite film again.
Fig. 1 is the surperficial SEM figure that the magnesium alloy of Micro-Arc Oxidized Ceramic Coating is contained on surface that test one step 4 obtains; Fig. 2 is the enlarged view of Fig. 1;
Fig. 3 is that the surface coverage that test one step 6 obtains has the surperficial SEM of the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film to scheme; Fig. 4 is the enlarged view of Fig. 3;
From Fig. 1 and Fig. 2, magnesium alloy is after differential arc oxidation, and due to the impact of strong voltage electric discharge, Micro-Arc Oxidized Ceramic Coating surface exists a large amount of irregular cavernous structure; From Fig. 3 and Fig. 4, after graphene oxide is modified, Micro-Arc Oxidized Ceramic Coating surface defines the graphene oxide rete of one deck densification, and surperficial cavernous structure disappears.
Test one step 4 is obtained the magnesium alloy of surface containing Micro-Arc Oxidized Ceramic Coating to be mounted in epoxy resin, then carry out SEM test, as shown in Figure 5; Fig. 5 is the section S EM figure that the magnesium alloy of Micro-Arc Oxidized Ceramic Coating is contained on surface that test one step 4 obtains, and in Fig. 5,1 is magnesium alloy substrate, and 2 is differential arc oxidation film layer, and 3 is epoxy resin.
As can be seen from Figure 5, the Micro-Arc Oxidized Ceramic Coating of Mg alloy surface is approximately 15 μm, and be combined well with matrix, coating growth is even.
There is the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film to be mounted in epoxy resin the surface coverage that test one step 6 obtains, then carry out SEM test, as shown in Figure 6; Fig. 6 is that the surface coverage that test one step 6 obtains has the section S EM of the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film to scheme, and in Fig. 6,1 is magnesium alloy substrate, and 2 is graphene oxide rete, and 3 is differential arc oxidation film layer, and 4 is epoxy resin.
As can be seen from Figure 6, graphene oxide fills Micro-Arc Oxidized Ceramic Coating completely, and the thicknesses of layers of graphene oxide is 4 μm ~ 6 μm.
Use electrochemical workstation (Princeton-4000) instrument to the magnesium alloy in test one, Micro-Arc Oxidized Ceramic Coating and graphene oxide and arc differential oxide ceramic composite film are tested, and as shown in Figure 7, concrete data list in table 1.
Fig. 7 is dynamic potential polarization curve, and in Fig. 7,1 is the dynamic potential polarization curve of magnesium alloy, and 2 is the dynamic potential polarization curve of Micro-Arc Oxidized Ceramic Coating, and 3 is the dynamic potential polarization curve of graphene oxide and arc differential oxide ceramic composite film.
Table 1 magnesium alloy, Micro-Arc Oxidized Ceramic Coating and composite film potentiodynamic polarization thereof
Can draw from Fig. 7 and table 1, the matrix corrosion current density of magnesium alloy is 0.105mA/cm
2, after differential arc oxidization technique process, Corrosion Behaviors of Magnesium Alloys electric current is reduced to 67.2nA/cm
2, corrosion current reduces by 3 orders of magnitude, and Micro-Arc Oxidized Ceramic Coating corrosion potential is shuffled 0.22V; Corrosion resistance of magnesium alloy can significantly improve; The corrosion electric current density of graphene oxide and arc differential oxide ceramic composite film is 14.5nA/cm
2, be 1/5 of Micro-Arc Oxidized Ceramic Coating corrosion current, corrosion potential to be shuffled 0.24V than matrix, and corrosion resistance nature improves further; This also illustrates that graphene oxide is a kind of excellent corrosion resistant material, and the method for use-testing one can significantly improve corrosion resistance of magnesium alloy energy.
Claims (10)
1. prepare a method for graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface, it is characterized in that a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface completes according to the following steps:
One, magnesium alloy pre-treatment: use 180#SiC sand paper, 1000#SiC sand paper and 2000#SiC sand paper to carry out grinding process to magnesium alloy successively, obtain the magnesium alloy of surface-brightening;
Two, supersound process: the magnesium alloy of surface-brightening is immersed in acetone, supersound process 3min ~ 10min under ultrasonic power is 200W ~ 300W, obtains the magnesium alloy after supersound process;
Three, oil removing: first the magnesium alloy after supersound process being immersed in temperature is 60 DEG C ~ 75 DEG C, and concentration is 10min ~ 20min in the NaOH solution of 40g/L ~ 50g/L, obtains the magnesium alloy after NaOH solution process; Magnesium alloy after NaOH solution process being immersed in temperature is 60 DEG C ~ 75 DEG C, and concentration is 10min ~ 20min in the sodium radio-phosphate,P-32 solution of 10g/L ~ 20g/L, obtains the magnesium alloy after sodium radio-phosphate,P-32 solution process; Use distilled water to rinse 3 times ~ 5 times to the magnesium alloy after sodium radio-phosphate,P-32 solution process, re-use hair dryer and dry up, obtain the magnesium alloy after oil removing;
Four, differential arc oxidation: the magnesium alloy after oil removing is placed in the stainless steel electrolytic groove that electrolytic solution is housed, the magnesium alloy after oil removing is connected with the positive pole of power supply, as anode, stainless electrolyzer is connected with the negative pole of power supply, as negative electrode; Adopting pulse mao power source to power, is 0.5A/dm in current density
2~ 0.8A/dm
2, dutycycle be 10% ~ 40% and supply frequency be differential arc oxidation 5min ~ 15min under 500Hz ~ 2000Hz, obtain surface containing the magnesium alloy of Micro-Arc Oxidized Ceramic Coating;
Electrolytic solution described in step 4 is made up of water glass, potassium hydroxide and Sodium Fluoride, and solvent is water; The concentration of described electrolytic solution mesosilicic acid sodium is 20g/L ~ 40g/L, and the concentration of potassium hydroxide is 3g/L ~ 8g/L, and the concentration of Sodium Fluoride is 1g/L ~ 5g/L;
Five, prepare graphene oxide: joined by natural graphite powder at 0 DEG C in the mixing acid of sulfuric acid and nitric acid, then low whipping speed is stir under 80r/min ~ 150r/min, and by KMnO
4dividing joins in the mixing acid of sulfuric acid and nitric acid 2 times ~ 5 times; Low whipping speed is 100r/min ~ 200r/min and temperature is again stirring reaction 2h ~ 3h at 35 DEG C ~ 40 DEG C, then adds distilled water, then low whipping speed is stirring reaction 2h ~ 3h under 100r/min ~ 200r/min, then adds the H that massfraction is 1.8% ~ 2%
2o
2solution, obtains reaction solution; By reaction solution supersound process 24h ~ 30h under ultrasonic power is 200W ~ 400W, obtain suspension liquid; Successively functional quality mark be 5% HCl solution and distilled water 3 times ~ 5 times are washed to suspension liquid, obtain graphene oxide;
The mixing acid of the sulfuric acid described in step 5 and nitric acid be by massfraction be 91.79% ~ 93.81% sulfuric acid and massfraction be 6.19% ~ 9.21% nitric acid be mixed with and form; Described massfraction be 91.79% ~ 93.81% sulfuric acid and massfraction be the volume ratio of the nitric acid of 6.19% ~ 9.21% be 150:(13 ~ 20);
The volume ratio of the mixing acid of the quality of the natural graphite powder described in step 5 and sulfuric acid and nitric acid is 5g:(120mL ~ 130mL);
Natural graphite powder described in step 5 and KMnO
4mass ratio be 1:3;
The mixing acid of the sulfuric acid described in step 5 and nitric acid and the volume ratio of distilled water are 1:(2 ~ 3);
The mixing acid of the sulfuric acid described in step 5 and nitric acid and massfraction are the H of 1.8% ~ 2%
2o
2the volume ratio of solution is 1:(7 ~ 9);
Six, graphene oxide is joined in distilled water, obtain the graphene oxide solution that concentration is 1mg/L; Be that the graphene oxide solution of 1mg/L is coated in the Micro-Arc Oxidized Ceramic Coating of the magnesium alloy of surface containing Micro-Arc Oxidized Ceramic Coating by concentration, apply 3 ~ 5 times, dry 1h ~ 2h at temperature is 40 DEG C ~ 50 DEG C, obtains the magnesium alloy that surface coverage has graphene oxide and arc differential oxide ceramic composite film again.
2. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the magnesium alloy described in step one is ZK60 magnesium alloy.
3. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the thickness being coated with graphene oxide rete in the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film described in step 6 is 4 μm ~ 6 μm.
4. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the thickness being coated with Micro-Arc Oxidized Ceramic Coating in the magnesium alloy of graphene oxide and arc differential oxide ceramic composite film described in step 6 is 13 μm ~ 20 μm.
5. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, it is characterized in that in step 4, the magnesium alloy after oil removing being placed in the stainless steel electrolytic groove that electrolytic solution is housed, magnesium alloy after oil removing is connected with the positive pole of power supply, as anode, stainless electrolyzer is connected with the negative pole of power supply, as negative electrode; Adopting pulse mao power source to power, is 0.6A/dm in current density
2~ 0.7A/dm
2, dutycycle be 10% ~ 40% and supply frequency be differential arc oxidation 5min ~ 10min under 1000Hz ~ 2000Hz, obtain surface containing the magnesium alloy of Micro-Arc Oxidized Ceramic Coating.
6. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the electrolytic solution described in step 4 is made up of water glass, potassium hydroxide and Sodium Fluoride, and solvent is water; The concentration of described electrolytic solution mesosilicic acid sodium is 25g/L ~ 35g/L, and the concentration of potassium hydroxide is 4g/L ~ 6g/L, and the concentration of Sodium Fluoride is 2g/L ~ 4g/L.
7. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, it is characterized in that the mixing acid of the sulfuric acid described in step 5 and nitric acid be by massfraction be 92% ~ 93% sulfuric acid and massfraction be 7% ~ 8% nitric acid be mixed with and form; Described massfraction be 92% ~ 93% sulfuric acid and massfraction be the volume ratio of the nitric acid of 7% ~ 8%% be 150:(13 ~ 18).
8. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the volume ratio of the quality of the natural graphite powder described in step 5 and the mixing acid of sulfuric acid and nitric acid is 5g:(120mL ~ 125mL).
9. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the mixing acid of the sulfuric acid described in step 5 and nitric acid and the volume ratio of distilled water are 1:(2 ~ 2.5).
10. a kind of method preparing graphene oxide and arc differential oxide ceramic composite film at Mg alloy surface according to claim 1, is characterized in that the mixing acid of the sulfuric acid described in step 5 and nitric acid and massfraction are the H of 1.8% ~ 2%
2o
2the volume ratio of solution is 1:(7 ~ 8).
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| CN105239134A (en) * | 2015-11-11 | 2016-01-13 | 赣南师范学院 | Method for improving corrosion resistance of magnesium alloy anode oxide film layer |
| CN105350049A (en) * | 2015-11-23 | 2016-02-24 | 桂林理工大学 | Preparing method for graphene oxide composite coating on surface of magnesium alloy |
| CN105624664A (en) * | 2016-03-15 | 2016-06-01 | 赣南师范学院 | Hole sealing method for magnesium alloy surface rare earth chemical conversion coating |
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| CN105350049A (en) * | 2015-11-23 | 2016-02-24 | 桂林理工大学 | Preparing method for graphene oxide composite coating on surface of magnesium alloy |
| CN105350049B (en) * | 2015-11-23 | 2017-12-12 | 桂林理工大学 | A kind of preparation method of Mg alloy surface graphene oxide composite coating |
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| CN109898122A (en) * | 2019-04-12 | 2019-06-18 | 桂林理工大学 | Magnesium alloy surface micro-arc oxidation/graphene oxide composite film preparation method |
| CN110079850A (en) * | 2019-04-23 | 2019-08-02 | 苏州紫金港智能制造装备有限公司 | The method for improving Mg alloy surface corrosion resisting property based on differential arc oxidation and laser remolten |
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