CN109811385B - Polyvinylidene fluoride/aluminum oxide composite film on surface of aluminum and aluminum alloy and preparation method thereof - Google Patents
Polyvinylidene fluoride/aluminum oxide composite film on surface of aluminum and aluminum alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy and a preparation method thereof, wherein zirconium salt is introduced into a solution by utilizing micro-arc oxidation to generate zirconium oxide in a ceramic film; polyvinylidene fluoride is introduced into the ceramic membrane to generate a polyvinylidene fluoride coating, so that micropores in the micro-arc oxidation ceramic membrane are sealed, the cross section and the surface tension/wetting angle of the ceramic membrane and a corrosive medium are changed, the performances of alkali resistance, acid corrosion resistance and the like of the coating are improved, the obtained polyvinylidene fluoride/aluminum oxide composite membrane on the surface of aluminum and aluminum alloy is resistant to neutral NaCl salt mist corrosion for more than 500h, the microhardness is up to 950Hv, the pressure resistance is 1000V, the insulation resistance is up to 495M omega, the alkali drop corrosion time is up to more than 227s, and the composite membrane has no special requirements on the material, shape, size and the like of aluminum or aluminum alloy and has wide applicability.
Description
Technical Field
The invention relates to the technical field of metal material surface treatment, in particular to a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy and a preparation method thereof.
Background
Aluminum alloy is one of the most widely used alloys in modern industry. By adding a certain amount of copper, silicon, aluminum, zinc, manganese and a small amount of elements such as nickel, iron, titanium, chromium, lithium and the like into the aluminum matrix, the aluminum alloy can have higher strength while keeping the advantages of light weight and the like of pure aluminum. Therefore, the specific strength of the alloy steel is superior to that of a plurality of alloy steels, so that the alloy steel becomes an ideal structural material and is widely applied to the aspects of aviation, aerospace, automobiles, mechanical manufacturing, ships, chemical industry and the like, for example, fuselages, skins, air compressors and the like of airplanes, which are often made of aluminum alloy, so as to reduce the self weight. The aluminum alloy is adopted to replace the welding of steel plate materials, and the weight of the structure can be reduced by more than 50%. Because the aluminum alloy has low density but higher strength which is close to or exceeds that of high-quality steel, the plasticity is good, and the aluminum alloy can be processed into various sectional materials; meanwhile, the composite material has the advantages of excellent electrical conductivity, thermal conductivity, corrosion resistance and the like.
The micro-arc oxidation process is a surface treatment process of non-ferrous metals (such as aluminum, titanium, and the like) developed in recent years, and particularly since the nineties of the twentieth century, the process has become a research hotspot of the national academia and is gradually accepted by the industry. Particularly, the micro-arc oxidation treatment of the aluminum alloy surface, because of the high hardness, scratch resistance, corrosion resistance and other capabilities of the micro-arc oxidation ceramic layer, the technology is widely applied to the surface treatment of aluminum alloy products.
At present, when the aluminum alloy is subjected to micro-arc oxidation, a silicate, phosphate and metaaluminate solution system is mostly adopted, and the hardness, the wear resistance and the like of the prepared ceramic membrane are obviously improved; however, the ceramic film prepared on the surface of the aluminum alloy is amphoteric oxide, and is neither acid corrosion resistant nor alkali corrosion resistant.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy and a preparation method thereof, wherein zirconium salt is introduced into a solution by micro-arc oxidation to generate zirconium oxide in a ceramic film; polyvinylidene fluoride is introduced into the ceramic membrane to generate a polyvinylidene fluoride coating, so that micropores in the micro-arc oxidation ceramic membrane are sealed, the cross section and the surface tension/wetting angle of the ceramic membrane and a corrosive medium are changed, the performances of alkali resistance, acid corrosion resistance and the like of the coating are improved, the neutral NaCl salt mist corrosion resistance of the obtained polyvinylidene fluoride/aluminum oxide composite membrane on the surface of aluminum and aluminum alloy is up to more than 500h, the microhardness is up to 950Hv, the pressure resistance is 1000V, the insulation resistance is up to 495M omega, and the alkali drop corrosion time is up to more than 227 s.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy comprises the following raw materials: polyvinylidene fluoride solution, ammonium fluorozirconate, sodium dihydrogen phosphate, sodium hexametaphosphate, borax and water.
Preferably, the solvent of the polyvinylidene fluoride solution is dimethyl sulfoxide.
Preferably, the raw materials are used in the following amounts: 100-250 parts of polyvinylidene fluoride solution, 5-50 parts of ammonium fluorozirconate, 20-30 parts of sodium dihydrogen phosphate, 14-20 parts of sodium hexametaphosphate and 15-25 parts of borax.
Preferably, the volume ratio of the polyvinylidene fluoride solution to water is as follows: (0.1-0.25): 1.
preferably, the concentration of polyvinylidene fluoride in the polyvinylidene fluoride solution is 10-50 g/L.
(II) a preparation method of the polyvinylidene fluoride/aluminum oxide composite membrane on the surface of the aluminum and the aluminum alloy, which comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution;
and 3, carrying out ultrasonic dispersion and micro-arc oxidation on the zirconium salt system solution to obtain the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and the aluminum alloy.
Preferably, in step 2, the pH value is adjusted by using sodium citrate.
Preferably, in the step 3, the frequency of the ultrasonic dispersion is 40KHZ, the temperature of the ultrasonic dispersion is 15-25 ℃, and the time of the ultrasonic dispersion is 30 min.
Preferably, in step 3, the micro-arc oxidation method comprises: the zirconium salt system solution is placed in a micro-arc oxidation treatment tank to serve as a micro-arc oxidation electrolyte, aluminum or aluminum alloy is placed in the micro-arc oxidation electrolyte to serve as an anode, a stainless steel plate is placed in the micro-arc oxidation electrolyte to serve as a cathode, and a micro-arc oxidation pulse power supply is adopted to perform micro-arc oxidation under the conditions that the pulse frequency is 100-2000 Hz and the duty ratio is 5-50%.
Preferably, in the step 3, the pulse frequency of the micro-arc oxidation is 500-700 Hz, and the duty ratio of the micro-arc oxidation is 15-30%.
Preferably, in the step 3, the temperature of the micro-arc oxidation is 10-50 ℃, and the time of the micro-arc oxidation is 15-65 min.
Preferably, in the step 3, the aluminum or the aluminum alloy is firstly subjected to micro-arc oxidation for 5min under the condition that the voltage is 50-250V, and then the voltage is increased to 300-450V and then the micro-arc oxidation is continued for 10-60 min.
Compared with the prior art, the invention has the beneficial effects that:
1) in the preparation method of the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and the aluminum alloy, zirconium ions are added into the micro-arc oxidation electrolyte, and the micro-arc oxidation process is optimized,the polyvinylidene fluoride organic matter is combined with micro-arc oxidation, so that polyvinylidene fluoride/aluminum oxide (Al) grows on the surface of aluminum or aluminum alloy in situ2O3) Composite ceramic membrane, fully utilizes ZrO2Excellent corrosion resistance, hole sealing effect of polyvinylidene fluoride and improvement of corrosion resistance of the ceramic membrane. The obtained polyvinylidene fluoride/aluminum oxide composite membrane on the surface of the aluminum and aluminum alloy has neutral NaCl salt mist corrosion resistance of more than 500h, microhardness of more than 950Hv, voltage resistance of 1000V, insulation resistance of more than 495M omega and alkali drop corrosion time of 227 s.
While the ceramic membrane on the surface of the aluminum and aluminum alloy prepared by adopting the traditional micro-arc oxidation solution such as silicate, aluminate, phosphate and the like has the neutral NaCl salt mist corrosion resistance time of less than 300h, alkali drop corrosion time of less than 30s and pressure resistance of 500V, thereby showing that the polyvinylidene fluoride/Al treated by the micro-arc oxidation method is subjected to the micro-arc oxidation treatment2O3The composite film has excellent effect.
(2) The invention can obtain smooth and compact polyvinylidene fluoride/Al on the surface of aluminum or aluminum alloy2O3A composite ceramic membrane. When the thickness of the ceramic film is within 30 mu m, the surface roughness (Ra) of the ceramic film is less than 1 mu m, and the surface roughness of the aluminum or aluminum alloy workpiece is not increased under normal conditions; microscopic structure analysis shows that the average diameter of micropores on the surface of the ceramic membrane is less than 2 microns, the diameter of the micropores is reduced along with the increase of the thickness of the ceramic membrane, and the growth of the ceramic membrane has a self-closing tendency.
The surface roughness and the micropore diameter of the ceramic membrane on the surface of the aluminum and the aluminum alloy prepared by the traditional micro-arc oxidation solution and the micro-arc oxidation process are increased along with the increase of the thickness of the ceramic membrane.
(3) The continuous service life of the zirconium salt system solution used in the invention is up to more than 6 months; the system solution does not contain metal ions such as high-valence chromium which seriously pollute the environment, and the service life is long, so the system solution has the advantages of stability, long acting, environmental protection.
(4) The invention has no special requirements on the material, shape, size and the like of the aluminum or the aluminum alloy, and the uniform and compact ceramic membrane can be obtained on the surface of the aluminum or the aluminum alloy immersed in the solution of the zirconium salt system after the micro-arc oxidation treatment, so the invention has wide applicability.
Drawings
The invention is described in further detail below with reference to the figures and specific embodiments.
FIG. 1 is an external view of an aluminum alloy of example 1; wherein, the figure (a) is an appearance figure of the aluminum alloy before the micro-arc oxidation treatment; the figure (b) is an appearance figure of the aluminum alloy after the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution; FIG. (c) is an external view of the aluminum alloy after the micro-arc oxidation treatment;
FIG. 2 is a wetting angle diagram for the aluminum alloy of example 1; wherein, the graph (a) is a wetting angle graph of the aluminum alloy before micro-arc oxidation treatment; the graph (b) is a wetting angle graph of the aluminum alloy after the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution; FIG. c is a view showing the wetting angle of the aluminum alloy after the micro-arc oxidation treatment;
FIG. 3 is a graph of the aluminum alloy of example 1 before alkali drip etching; wherein, the picture (a) is a picture before the alkali drop corrosion of the aluminum alloy before the micro-arc oxidation treatment; the figure (b) is a figure before alkali drop corrosion of the aluminum alloy after micro-arc oxidation treatment without adding polyvinylidene fluoride solution; FIG. (c) is a diagram before alkali drop corrosion of the aluminum alloy after the micro-arc oxidation treatment;
FIG. 4 is a graph of the aluminum alloy of example 1 after alkali drip etching; wherein, the picture (a) is a picture after the alkali drop corrosion of the aluminum alloy before the micro-arc oxidation treatment; the figure (b) is a figure after alkali drop corrosion of the aluminum alloy after micro-arc oxidation treatment without adding polyvinylidene fluoride solution; FIG. (c) is a diagram after the alkali drop corrosion of the aluminum alloy after the micro-arc oxidation treatment;
FIG. 5 is a cross-sectional SEM image of the aluminum alloy of example 1 at 1000 Xmagnification; wherein, the figure (a) is a cross-section SEM image of a polyvinylidene fluoride/alumina composite membrane generated by micro-arc oxidation treatment; FIG. (b) is a sectional SEM image of the ceramic membrane generated by the micro-arc oxidation treatment without adding polyvinylidene fluoride solution;
FIG. 6 is a surface SEM image of the aluminum alloy of example 1 at 500 times magnification; wherein, the figure (a) is a surface SEM picture of the polyvinylidene fluoride/alumina composite ceramic membrane generated by the micro-arc oxidation treatment of the aluminum alloy, and the figure (b) is a surface SEM picture of the ceramic membrane generated by the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution;
FIG. 7 is a surface SEM image of the aluminum alloy of example 1 at 1000 and 1500 magnification; FIG. (a) is a surface SEM image of a polyvinylidene fluoride/alumina composite film produced by micro-arc oxidation treatment; the figure (b) is a surface SEM image of the ceramic membrane generated by the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution;
FIG. 8 is a line scan EDS spectrum of the aluminum alloy of example 1; wherein, the graph (a) is a line scanning EDS spectrogram of the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum alloy after the micro-arc oxidation treatment; figure (b) is a ceramic film line scanning EDS spectrogram generated by micro-arc oxidation treatment without adding polyvinylidene fluoride solution;
FIG. 9 is an XRD spectrum of the PVDF/alumina composite film on the surface of the aluminum alloy after the micro-arc oxidation treatment of the aluminum alloy in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 50 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine for ultrasonic dispersion for 30min under the conditions of the frequency of 40KHZ and the temperature of 25 ℃, then placing the solution in a micro-arc oxidation treatment tank to be used as micro-arc oxidation electrolyte, and placing a 2A12 aluminum alloy plate in a micro-arc oxidation treatment tankPlacing the stainless steel plate in a micro-arc oxidation electrolyte as an anode, placing the stainless steel plate in the micro-arc oxidation electrolyte as a cathode, then adopting a micro-arc oxidation pulse power supply, carrying out micro-arc oxidation treatment on the aluminum alloy plate under the conditions that the pulse frequency is 600Hz, the duty ratio is 15 percent and the temperature is 30 ℃, firstly carrying out micro-arc oxidation for 5min under the condition that the voltage is 200V, then continuing the micro-arc oxidation for 30min after the voltage is increased to 450V, and obtaining polyvinylidene fluoride/aluminum oxide (Al) on the surface of the aluminum alloy plate2O3) A composite membrane.
Example 2
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 40 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine, performing ultrasonic dispersion for 30min at the frequency of 40KHZ and the temperature of 20 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank to be used as micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte to be used as an anode, placing a stainless steel plate in the micro-arc oxidation electrolyte to be used as a cathode, then adopting a micro-arc oxidation pulse power supply, performing micro-arc oxidation treatment on the aluminum alloy plate under the conditions of the pulse frequency of 600Hz, the duty ratio of 15% and the temperature of 30 ℃, performing micro-arc oxidation for 5min under the condition of the voltage of 200V, then raising the voltage to 450V, and then continuing the micro-arc oxidation for 30min, thus obtaining the polyvinylidene fluoride/aluminum oxide2O3) A composite membrane.
Example 3
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 30 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine, performing ultrasonic dispersion for 30min at the frequency of 40KHZ and the temperature of 20 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank to be used as micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte to be used as an anode, placing a stainless steel plate in the micro-arc oxidation electrolyte to be used as a cathode, then adopting a micro-arc oxidation pulse power supply, performing micro-arc oxidation treatment on the aluminum alloy plate under the conditions of the pulse frequency of 600Hz, the duty ratio of 15% and the temperature of 30 ℃, performing micro-arc oxidation for 5min under the condition of the voltage of 200V, then raising the voltage to 450V, and then continuing the micro-arc oxidation for 30min, thus obtaining the polyvinylidene fluoride/aluminum oxide2O3) A composite membrane.
Example 4
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 20 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine, performing ultrasonic dispersion for 30min at the frequency of 40KHZ and the temperature of 25 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank to be used as micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte to be used as an anode, placing a stainless steel plate in the micro-arc oxidation electrolyte to be used as a cathode, then adopting a micro-arc oxidation pulse power supply, performing micro-arc oxidation treatment on the aluminum alloy plate under the conditions of the pulse frequency of 600Hz, the duty ratio of 15% and the temperature of 30 ℃, performing micro-arc oxidation for 5min under the condition of the voltage of 200V, then raising the voltage to 450V, and then continuing the micro-arc oxidation for 30min, thus obtaining the polyvinylidene fluoride/aluminum oxide2O3) A composite membrane.
Example 5
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 20 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine for ultrasonic dispersion for 30min at the frequency of 40KHZ and the temperature of 20 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank as a micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte as an anode, placing a stainless steel plate in the micro-arc oxidation electrolyte as a cathode, then adopting a micro-arc oxidation pulse power supply for micro-arc oxidation treatment of the aluminum alloy plate at the pulse frequency of 100Hz and the duty ratio of 5% and the temperature of 30 ℃, firstly micro-arc oxidizing for 5min at the voltage of 200V, then raising the voltage to 450V, and then continuing to perform micro-arc oxidation for 5minMicro-arc oxidation for 30min to obtain polyvinylidene fluoride/aluminum oxide (Al) on the surface of the aluminum alloy plate2O3) A composite membrane.
Example 6
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 20 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine, performing ultrasonic dispersion for 30min at the frequency of 40KHZ and the temperature of 25 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank to be used as a micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte to be used as an anode, placing a stainless steel plate in the micro-arc oxidation electrolyte to be used as a cathode, then adopting a micro-arc oxidation pulse power supply, performing micro-arc oxidation treatment on the aluminum alloy plate under the conditions of the pulse frequency of 2000Hz, the duty ratio of 50% and the temperature of 50 ℃, performing micro-arc oxidation for 5min under the condition of the voltage of 50V, then raising the voltage to 400V, and then continuing the micro-arc oxidation for 30min, thus obtaining the polyvinylidene fluoride/aluminum2O3) A composite membrane.
Example 7
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 40 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine, performing ultrasonic dispersion for 30min at the frequency of 40KHZ and the temperature of 25 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank to be used as a micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte to be used as an anode, placing a stainless steel plate in the micro-arc oxidation electrolyte to be used as a cathode, then adopting a micro-arc oxidation pulse power supply, performing micro-arc oxidation treatment on the aluminum alloy plate under the conditions of the pulse frequency of 500Hz, the duty ratio of 25% and the temperature of 50 ℃, performing micro-arc oxidation for 5min under the condition of the voltage of 150V, then raising the voltage to 300V, and then continuing the micro-arc oxidation for 10min, thus obtaining the polyvinylidene fluoride/aluminum2O3) A composite membrane.
Example 8
A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy comprises the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the concentration of 30 g/L.
Step 3, placing the zirconium salt system solution in an ultrasonic dispersion machine for ultrasonic dispersion for 30min under the conditions of the frequency of 40KHZ and the temperature of 25 ℃, then placing the zirconium salt system solution in a micro-arc oxidation treatment tank to be used as micro-arc oxidation electrolyte, placing a 2A12 aluminum alloy plate in the micro-arc oxidation electrolyte to be used as an anode, and placing a stainless steel plate in the micro-arc oxidation electrolyte to be used as a micro-arc oxidation electrolyteA cathode, a micro-arc oxidation pulse power supply is adopted, micro-arc oxidation treatment is carried out on the aluminum alloy plate under the conditions that the pulse frequency is 700Hz, the duty ratio is 30 percent and the temperature is 10 ℃, micro-arc oxidation is firstly carried out for 5min under the condition that the voltage is 250V, then the micro-arc oxidation is continued for 60min after the voltage is increased to 450V, and polyvinylidene fluoride/aluminum oxide (Al) is obtained on the surface of the aluminum alloy plate2O3) A composite membrane.
Table 1 shows the insulation resistance at different voltages for different samples before and after the treatment of example 1. When the insulation resistance is measured, one test wire of the megohmmeter is clamped on a riveted aluminum wire of a sample (a part without an oxide film is selected), and the other test wire of the megohmmeter is tightly contacted with the oxide film on the surface of the sample, wherein the contact area is about 50mm2The test was performed in a dry environment with an air humidity of less than 20%. Two voltage gears of 500V and 1000V are selected, the insulation resistance of the oxide film is tested in a subsection mode, and the test result is shown in table 1. As can be seen from Table 1, the withstand voltage and the insulation resistance of the aluminum alloy after the micro-arc oxidation treatment in example 1 are significantly improved.
TABLE 1 insulation resistance/M.OMEGA.for different samples at different voltages
Table 2 shows the alkali-drop corrosion times of various samples before and after the treatment of example 1. In that
About 10mg, 100g/L NaOH solution is dropped on the surface of the sample, and the drop is visually observed until corrosion bubbles are generated, wherein the corrosion through time of the oxide film is the corrosion resistance of the oxide film, and the test results are shown in Table 2. As shown in Table 2, the alkali corrosion resistance time of the aluminum alloy treated in example 1 is significantly increased, thereby illustrating that the polyvinylidene fluoride/Al formed on the surface of the aluminum alloy treated by the micro-arc oxidation process according to the present invention2O3The composite ceramic membrane has excellent alkali corrosion resistance.
TABLE 2 alkali drop erosion times for different samples
Table 3 shows the wetting angles with water of the various samples before and after the treatment in example 1. As can be seen from Table 3, in example 3, the wetting angle of the aluminum alloy after the micro-arc oxidation treatment is larger than that of the aluminum alloy without the addition of the polyvinylidene fluoride solution, and the porous structure of the film layer without the addition of the polyvinylidene fluoride solution is adopted, so that the polyvinylidene fluoride/Al generated on the surface of the aluminum alloy after the micro-arc oxidation treatment is shown in the invention2O3The holes of the composite ceramic membrane are better sealed.
TABLE 3 wetting Angle of different samples
Table 4 shows the microhardness of various samples before and after the treatment in example 1. The microhardness measurement adopts a microhardness meter to measure the microhardness of 2A12 aluminum alloy and a film layer obtained after micro-arc oxidation under different conditions, the applied load is 100gf, the load retention time is 15s, 3 points are randomly selected on the surface of a sample to measure and average, the microhardness (HV) value is calculated by measuring the length of two diagonal lines of an indentation and directly input, and the equipment directly calculates and outputs according to the following formula (1).
In the formula F-load applied in Newton (N)
d-the arithmetic average of the two indentation diagonal lengths d1 and d2 in millimeters (mm), with the test results shown in Table 4. As can be seen from Table 4, the micro-hardness of the aluminum alloy after the micro-arc oxidation treatment in example 1 is significantly improved.
TABLE 4 microhardness/HV of different samples
In the above tables 1 to 4, the substrate is the sample before micro-arc oxidation treatment, the micro-arc oxidation is the sample after micro-arc oxidation treatment without adding polyvinylidene fluoride solution, and the micro-arc oxidation composite film layer is the sample of the polyvinylidene fluoride/aluminum oxide composite film after micro-arc oxidation treatment in example 1.
FIG. 1 is an external view of an aluminum alloy before micro-arc oxidation treatment in example 1, after micro-arc oxidation treatment without addition of a polyvinylidene fluoride solution, and after micro-arc oxidation treatment in this example. As can be seen from FIG. 1, the surface of the aluminum alloy before the micro-arc oxidation treatment is smooth and has metallic luster; after the micro-arc oxidation treatment without the addition of the polyvinylidene fluoride solution and the micro-arc oxidation treatment in the embodiment, the luster of the surface of the aluminum alloy disappears, and the color and luster of the composite film on the surface of the aluminum alloy are uniform and consistent.
FIG. 2 is a graph of the wetting angle of the aluminum alloy before the micro-arc oxidation treatment in example 1, after the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution, and after the micro-arc oxidation treatment in this example.
FIG. 3 is a diagram of the aluminum alloy before the micro-arc oxidation treatment of example 1, after the micro-arc oxidation treatment without adding a polyvinylidene fluoride solution, and after the micro-arc oxidation treatment of this example before the alkali drop corrosion.
FIG. 4 is a diagram of the aluminum alloy after alkali drop corrosion before the micro-arc oxidation treatment of example 1, after the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution, and after the micro-arc oxidation treatment of this example.
FIG. 5 is a SEM image of the cross section of the polyvinylidene fluoride/aluminum oxide composite film formed by the micro-arc oxidation treatment of the aluminum alloy of example 1 and the cross section of the ceramic film formed by the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution, with the magnification of 1000 times. As shown in FIG. 5, a layer of polyvinylidene fluoride/Al with a thickness of about 20um is formed on the surface of the aluminum alloy subjected to the micro-arc oxidation treatment and the surface of the aluminum alloy not added with the polyvinylidene fluoride solution2O3A composite ceramic membrane. The interface of the composite ceramic membrane and the aluminum alloy matrix is tightly combined without obvious defects, the shape of the interface is wavy, and the composite ceramic membrane and the aluminum alloy matrix are firmly combined together in a dog-tooth staggered state, so that the micro-arc oxidation treatment of the invention is proved that the composite ceramic membrane and the aluminum alloy matrix are generated on the surface of the aluminum alloyPolyvinylidene fluoride/Al2O3The composite film has excellent bonding performance with the aluminum alloy matrix.
FIG. 6 is an SEM image of the cross section of the composite ceramic membrane produced by the micro-arc oxidation treatment of the aluminum alloy of example 1 and the surface of the ceramic membrane produced by the micro-arc oxidation treatment without adding polyvinylidene fluoride solution, with a magnification of 500 times. As can be seen from FIG. 6, a ceramic film with micropores is formed on the surface of the aluminum alloy after the micro-arc oxidation treatment without the addition of the polyvinylidene fluoride solution, and the pore diameter of the micropores is smaller, and the average pore diameter is smaller than 2 μm. In the embodiment, most of the micropores of the ceramic membrane formed on the surface of the aluminum alloy after the micro-arc oxidation treatment are blocked by the polyvinylidene fluoride solution.
FIG. 7 is SEM images of the cross section of the polyvinylidene fluoride/aluminum oxide composite film formed by the micro-arc oxidation treatment of the aluminum alloy of example 1 and the surface of the ceramic film formed by the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution, wherein the magnification is 1000 times and 1500 times. As can be seen from FIG. 7, a ceramic film with micropores is formed on the surface of the aluminum alloy after the micro-arc oxidation treatment without the addition of the polyvinylidene fluoride solution, and the pore diameter of the micropores is smaller, and the average pore diameter is smaller than 2 μm. In the embodiment, most of the micropores of the ceramic membrane formed on the surface of the aluminum alloy after the micro-arc oxidation treatment are blocked by the polyvinylidene fluoride solution.
FIG. 8 is a line scanning EDS spectrogram of a cross section of the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum alloy after the micro-arc oxidation treatment and a ceramic film generated by the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution in example 1. As can be seen from FIG. 8, polyvinylidene fluoride/Al formed on the surface of the aluminum alloy after the micro-arc oxidation treatment in the present example2O3The composite ceramic membrane mainly comprises Zr, O, F, P and Al elements, and the micro-arc oxidation electrolyte does not contain the Al element, so the Al element in the composite ceramic membrane is from an aluminum alloy matrix. In contrast, since the aluminum alloy matrix does not contain Zr element, the Zr element in the composite ceramic film should come from the zirconium salt system solution. Therefore, the zirconium salt is added into the micro-arc oxidation electrolyte, and the ceramic membrane containing Zr element can be obtained on the surface of aluminum and aluminum alloy. The F element in the ceramic membrane generated by the micro-arc oxidation treatment without adding the polyvinylidene fluoride solution comes from the polyvinylidene fluoride solution, so the table shows that the F element is not strictThe polyvinylidene fluoride solution is added in the micro-arc oxidation, so that the composite ceramic membrane containing the polyvinylidene fluoride on the surfaces of aluminum and aluminum alloy can be realized.
FIG. 9 is an XRD spectrum of the PVDF/alumina composite film on the surface of the aluminum alloy after the micro-arc oxidation treatment in example 1.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A preparation method of a polyvinylidene fluoride/aluminum oxide composite film on the surface of aluminum and aluminum alloy is characterized by comprising the following steps:
step 1, dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution;
step 2, adding ammonium fluorozirconate, a polyvinylidene fluoride solution, sodium dihydrogen phosphate, sodium hexametaphosphate and borax into water, uniformly stirring, and adjusting the pH value to 6-7 to obtain a zirconium salt system solution;
and 3, carrying out ultrasonic dispersion and micro-arc oxidation on the zirconium salt system solution to obtain the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and the aluminum alloy.
2. The method for preparing the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy according to claim 1, wherein the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy comprises the following raw materials in parts by weight: 100-250 parts of polyvinylidene fluoride solution, 5-50 parts of ammonium fluorozirconate, 20-30 parts of sodium dihydrogen phosphate, 14-20 parts of sodium hexametaphosphate and 15-25 parts of borax.
3. The method for preparing the polyvinylidene fluoride/aluminum oxide composite membrane on the surface of the aluminum and aluminum alloy according to claim 1, wherein the volume ratio of the polyvinylidene fluoride solution to water is (0.1-0.25): 1.
4. the method for preparing the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy according to claim 3, wherein the concentration of polyvinylidene fluoride in the polyvinylidene fluoride solution is 10-50 g/L.
5. The method for preparing the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy according to claim 1, wherein in the step 2, the pH value is adjusted by sodium citrate.
6. The method for preparing the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy according to claim 1, wherein in the step 3, the micro-arc oxidation method comprises the following steps: the zirconium salt system solution is placed in a micro-arc oxidation treatment tank to serve as a micro-arc oxidation electrolyte, aluminum or aluminum alloy is placed in the micro-arc oxidation electrolyte to serve as an anode, a stainless steel plate is placed in the micro-arc oxidation electrolyte to serve as a cathode, and a micro-arc oxidation pulse power supply is adopted to perform micro-arc oxidation under the conditions that the pulse frequency is 100-2000 Hz and the duty ratio is 5-50%.
7. The method for preparing the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy according to claim 6, wherein in the step 3, the micro-arc oxidation temperature is 10-50 ℃, and the micro-arc oxidation time is 15-65 min.
8. The method for preparing the polyvinylidene fluoride/aluminum oxide composite film on the surface of the aluminum and aluminum alloy according to claim 7, wherein in the step 3, the aluminum or aluminum alloy is firstly subjected to micro-arc oxidation for 5min under the condition that the voltage is 50-250V, and then the micro-arc oxidation is continued for 10-60 min after the voltage is increased to 300-450V.
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