CN115807213A - Magnesium alloy surface super-hydrophobic composite film layer and preparation method thereof - Google Patents
Magnesium alloy surface super-hydrophobic composite film layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnesium alloy surface super-hydrophobic composite film and a preparation method thereof, and relates to the technical field of magnesium alloy surface treatment. The invention adopts a magnetron sputtering method, combines argon ion etching and sequentially sputters an AlSi layer and SiO on the surface of the magnesium alloy 2 Layer of AlSi/SiO 2 Composite film layer, prepared AlSi/SiO 2 The combination of the film and the magnesium alloy matrix is good, no obvious pore is formed on the surface of the film, the surface roughness is obviously reduced compared with the roughness of the film prepared by a micro-arc oxidation method, a nano-scale microstructure is generated on the surface of the film, the wetting contact angle of the film is obviously larger and reaches 157.5 degrees, and the film has an obvious super-hydrophobic characteristic.
Description
Technical Field
The invention relates to the technical field of magnesium alloy surface treatment, in particular to a magnesium alloy surface super-hydrophobic composite film layer and a preparation method thereof.
Background
The magnesium alloy has light weight and density of only 1.7kg/m 3 2/3 of aluminum and 1/4 of steel, has good castability and dimensional stability, easy processing, low rejection rate and good damping coefficient, has larger vibration damping capacity than aluminum alloy and cast iron, is very suitable for the production of automobiles, and has wide application space in the fields of aerospace, portable computers, mobile phones, electrical appliances, sports equipment and the like. However, because of high chemical activity and easy oxidation, the surface is easy to corrode in the using process, and the wide application of the magnesium alloy in the fields of aerospace, portable computers, mobile phones, electrical appliances, sports equipment and the like is greatly limited.
Because the corrosion resistance of magnesium alloy is poor, a certain surface treatment process is usually required to improve the surface corrosion resistance of the magnesium alloy. The common surface treatment method of the magnesium alloy comprises electroplating, chemical conversion, anodic oxidation, micro-arc oxidation and the like, wherein micro-arc oxidation (MAO) is used as a newer surface treatment process, and a ceramic film layer can be generated in situ on the surface of the magnesium alloy, so that the corrosion resistance of the magnesium alloy can be improved to a certain extent. However, the micro-arc oxidation film layer has certain pores on the surface, has high roughness and high hydrophilicity, so the improvement of the corrosion resistance of the magnesium alloy is limited.
The preparation of the super-hydrophobic composite film layer can promote the application of the magnesium alloy in other aspects of the super-hydrophobic field.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a magnesium alloy surface super-hydrophobic composite film layer and a preparation method thereof. Adopting a magnetron sputtering method to sequentially sputter and deposit an AlSi layer and SiO on the surface of the magnesium alloy 2 Layer of AlSi/SiO 2 A composite film layer of said AlSi/SiO 2 The film layer has good super-hydrophobic performance, not only can improve the corrosion resistance of the magnesium alloy, but also can promote the application of the magnesium alloy in other aspects of the super-hydrophobic field.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a magnesium alloy surface super-hydrophobic composite film layer, which comprises the following steps:
(1) Performing surface pretreatment on a magnesium alloy sample;
(2) Sputtering an AlSi layer on the magnesium alloy sample subjected to surface pretreatment in the step (1) by adopting an Al target and a Si target;
(3) Replacing the Al target with a Si target, and sputtering SiO on the magnesium alloy sample with the AlSi layer attached to the surface in the step (2) 2 And taking out the magnesium alloy sample to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Preferably, in the step (1), the magnesium alloy is one of AZ31, AM60, AZ91D or WE 43.
Preferably, in the step (1), the method for pretreating the surface of the magnesium alloy sample comprises the following steps: and sequentially grinding the magnesium alloy sample by using 400#, 800# and 1500# abrasive paper, polishing, sequentially putting into acetone, deionized water and absolute ethyl alcohol, ultrasonically cleaning for 3-10 min, and drying.
Preferably, the purity of the Al target and the Si target is more than or equal to 99.99 percent.
Preferably, in the step (2), the method for sputtering the AlSi layer is as follows: and (2) putting the magnesium alloy sample subjected to surface pretreatment obtained in the step (1) into a magnetron sputtering vacuum chamber, alternately putting two Al target materials and two Si target materials into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, vacuumizing, introducing argon, carrying out sputtering cleaning on the target materials, adjusting the flow of the argon and the air pressure of the vacuum chamber after the sputtering cleaning of the target materials is finished, and carrying out magnetron sputtering of an AlSi layer on the surface of the magnesium alloy sample by combining argon ion etching.
Further preferably, the purity of the argon is more than or equal to 99.999 percent.
Further preferably, the target sputtering cleaning parameters are as follows: degree of vacuum1×10 -4 ~5×10 -4 Pa, the argon flow is 100 to 250sccm, and the sputtering cleaning time is 5 to 30min.
Further preferably, the parameters of sputtering the AlSi layer are: the argon flow is 30 to 60sccm, the vacuum chamber pressure is 0.8 to 1.5Pa, the sputtering power is 30 to 150W, and the sputtering temperature is room temperature.
Further preferably, the argon ion etching treatment comprises: firstly sputtering AlSi for 10-20 min, then sputtering by argon ions for 1-5 min, then continuously sputtering AlSi for 10-20 min, then sputtering by argon ions for 1-5 min, and repeating the steps for 5-10 times.
Preferably, in the step (3), siO is magnetically sputtered 2 The method of the layer is as follows: adjusting the distance between the target and the magnesium alloy sample with the AlSi layer attached to the surface prepared in the step (2) to be 100mm, vacuumizing, introducing argon, carrying out sputtering cleaning on the target, adjusting the flow rate of the argon and the air pressure of a vacuum chamber after the sputtering cleaning of the target is finished, simultaneously introducing oxygen, and carrying out magnetron sputtering on the surface of the magnesium alloy sample with the AlSi layer attached to the surface prepared in the step (2) to obtain SiO 2 And (3) a layer.
Further preferably, the purity of the argon is more than or equal to 99.999 percent.
Further preferably, the target sputtering cleaning parameters are as follows: degree of vacuum 1X 10 -4 ~5×10 -4 Pa, argon flow rate of 100 to 250sccm, and sputtering cleaning time of 5 to 30min.
Further preferably, the oxygen purity is more than or equal to 99.999 percent.
Further preferably, siO is sputtered 2 The parameters of the layers are: argon flow rate of 20 to 40sccm, flow rate ratio of argon to oxygen (5 to 10): 1, the air pressure of a vacuum chamber is 0.7 to 2.0Pa, the sputtering power is 40 to 200W, the sputtering temperature is room temperature, and the sputtering time is 50 to 150min.
The invention provides a magnesium alloy surface super-hydrophobic composite film layer, which is formed by sequentially arranging an AlSi layer and SiO layer from inside to outside on a magnesium alloy substrate 2 Layer of AlSi/SiO 2 And (5) compounding the film layer.
The invention has the beneficial effects that:
1. the invention adopts a magnetron sputtering method to deposit and generate AlSi/SiO with super-hydrophobicity on the surface of the magnesium alloy 2 And (5) film layer. Because the argon ion etching is combined in the process of forming the AlSi layer by magnetron sputtering and the characteristics that Al and Si are easy to combine with matrix Mg atoms and O atoms in the atomic structure, the film layer and the magnesium alloy matrix have good combination, and the good combination in the film layer is also ensured.
2. The invention adopts the AlSi/SiO prepared by the magnetron sputtering method 2 The surface of the film layer has no obvious pores and small surface roughness, and simultaneously generates nano SiO 2 The microstructure and the wetting contact angle of the film layer are obviously larger and reach 157.5 degrees, so that the surface of the film layer has better super-hydrophobic performance, thereby better hindering the corrosion of a corrosion medium in the environment to the magnesium alloy matrix and promoting other applications of the magnesium alloy in the super-hydrophobic field.
Drawings
FIG. 1: alSi/SiO solid obtained in example 1 2 Scanning electron microscope photographs of the membrane layer and the MAO membrane layer obtained in comparative example 1, wherein a is the micro-morphology of the MAO membrane layer surface, and b is AlSi/SiO 2 Microscopic appearance of the surface of the film layer;
FIG. 2: alSi/SiO obtained in example 1 2 The membrane layer and the micro three-dimensional profile of the MAO membrane layer obtained in the comparative example 1;
FIG. 3: alSi/SiO obtained in example 2 2 Membrane layer, MAO membrane layer from comparative example 1, alSi membrane layer from comparative example 2, and SiO membrane layer from comparative example 3 2 Testing results of wettability contact angles of the surface of the film layer;
FIG. 4: alSi/SiO obtained in example 2 2 Film layer, MAO film layer obtained in comparative example 1, alSi film layer obtained in comparative example 2, siO film layer obtained in comparative example 3 2 Potentiodynamic polarization test curves of the film layer and the magnesium alloy matrix of the control group.
Detailed description of the preferred embodiments
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background art, because magnesium alloy has high chemical activity and is easy to oxidize, corrosion is very easy to occur in the using process, and a certain surface treatment process is needed to improve the surface corrosion resistance in the actual using process.
Based on the above, the invention provides a magnesium alloy surface super-hydrophobic composite film layer based on magnetron sputtering and a preparation method thereof. Combining argon ion etching in the magnetron sputtering process to prepare AlSi/SiO on the surface of the magnesium alloy 2 The super-hydrophobic composite film layer has no obvious pores on the surface, small surface roughness and nano SiO generated 2 Microstructure, alSi/SiO 2 The wetting contact angle of the super-hydrophobic composite film layer can reach 157.5 degrees.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention were all conventional in the art and commercially available.
Example 1: preparation of magnesium alloy surface super-hydrophobic composite film layer
(1) Grinding an AZ91D magnesium alloy sample by using 400#, 800#, 1500# abrasive paper in sequence, polishing, then putting into acetone, deionized water and absolute ethyl alcohol in sequence, cleaning for 5min by ultrasonic waves respectively, and drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, alternately putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, and vacuumizing to the vacuum degree of 1.5 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 150sccm, and carrying out sputtering cleaning on the Al target material and the Si target material for 15min;
after the sputtering and cleaning of the target material are finished, adjusting the air pressure of a vacuum chamber to be 1.0Pa, adjusting the flow of argon to be 40sccm, combining with argon ion etching, and carrying out magnetron sputtering on the magnesium alloy subjected to the surface treatment in the step (1) to form an AlSi layer at the sputtering power of 40W and the room temperature;
wherein, the argon ion etching treatment comprises the following steps: firstly sputtering AlSi for 10min, then sputtering argon ions for 2min, then continuing sputtering AlSi for 10min, then sputtering argon ions for 2min, and repeating the steps for 6 times;
(3) Opening a magnetron sputtering vacuum chamber, replacing the two Al targets with Si targets with the purity of 99.99%, adjusting the distance between the target and the magnesium alloy sample which is prepared in the step (2) and is provided with the AlSi layer on the surface to be 100mm, and vacuumizing to be 1.5 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 150sccm, and carrying out sputtering cleaning on the Si target material for 15min;
after the sputtering cleaning of the target material is finished, the air pressure of the vacuum chamber is adjusted to be 1.0Pa, the argon flow is 40sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 5:1, carrying out magnetron sputtering on the surface of the magnesium alloy sample with the AlSi layer attached to the surface in the step (2) at room temperature and under the condition that the sputtering power is 65W 2 And (3) taking out a magnesium alloy sample after the magnetron sputtering time is 60min to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Example 2: preparation of super-hydrophobic composite film layer on surface of magnesium alloy
(1) Grinding an AZ91D magnesium alloy sample by using 400#, 800#, 1500# abrasive paper in sequence, polishing, then putting into acetone, deionized water and absolute ethyl alcohol in sequence, cleaning for 4min by ultrasonic waves respectively, and drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, and vacuumizing until the vacuum degree is 2 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 130sccm, and carrying out sputtering cleaning on the Al target material and the Si target material for 20min;
after the sputtering cleaning of the target material is finished, regulating the air pressure of a vacuum chamber to be 1.0Pa, regulating the flow of argon to be 35sccm, combining with argon ion etching, and carrying out magnetron sputtering on the magnesium alloy subjected to surface treatment to form an AlSi layer at the sputtering power of 50W and the room temperature;
wherein, the argon ion etching treatment comprises the following steps: sputtering AlSi for 15min, then sputtering argon ions for 3min, then continuing sputtering AlSi for 15min, then sputtering argon ions for 3min, and repeating the steps for 5 times;
(3) Opening a magnetron sputtering vacuum chamber, replacing two Al targets with Si targets with the purity of 99.99 percent, adjusting the distance between the target and the magnesium alloy sample with the surface attached with the AlSi layer prepared in the step (2) to be 100mm, and vacuumizing to be 2 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 130sccm, and carrying out sputtering cleaning on the Si target material for 20min;
after the sputtering cleaning of the target material is finished, the air pressure of the vacuum chamber is adjusted to be 1.0Pa, the argon flow is 40sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 6:1, carrying out magnetron sputtering on a layer of SiO on the surface of the magnesium alloy sample with the AlSi film attached to the surface in the step (2) at room temperature and the sputtering power of 80W 2 And (3) taking out a magnesium alloy sample after the magnetron sputtering time is 70min to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Example 3: preparation of magnesium alloy surface super-hydrophobic composite film layer
(1) Sequentially grinding an AZ91D magnesium alloy sample by using 400#, 800# and 1500# abrasive paper, then polishing, sequentially putting into acetone, deionized water and absolute ethyl alcohol, respectively performing ultrasonic cleaning for 3min, and blow-drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, and vacuumizing until the vacuum degree is 3 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, and carrying out sputtering cleaning on the Al target material and the Si target material for 15min, wherein the flow of the argon is 120 sccm;
after the sputtering cleaning of the target material is finished, regulating the air pressure of a vacuum chamber to be 1.1Pa, regulating the flow of argon to be 45sccm, combining with argon ion etching, and carrying out magnetron sputtering on the magnesium alloy subjected to surface treatment to form an AlSi layer at the sputtering power of 60W and the room temperature;
wherein, the argon ion etching treatment comprises the following steps: firstly sputtering AlSi for 10min, then sputtering argon ions for 4min, then continuing sputtering AlSi for 10min, then sputtering argon ions for 4min, and repeating the steps for 5 times;
(3) Opening a magnetron sputtering vacuum chamber, replacing two Al targets with Si targets with the purity of 99.99 percent, adjusting the distance between the target and the magnesium alloy sample with the surface attached with the AlSi layer prepared in the step (2) to be 100mm, and vacuumizing to be 3 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, and carrying out sputtering cleaning on the Si target for 15min, wherein the flow of the argon is 120 sccm;
after the sputtering cleaning of the target material is finished, the air pressure of the vacuum chamber is adjusted to be 1.0Pa, the argon flow is 30sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 7:1, carrying out magnetron sputtering on the surface of the magnesium alloy sample with the AlSi film attached to the surface in the step (2) at room temperature and the sputtering power of 100W to obtain SiO 2 And (3) taking out a magnesium alloy sample after the magnetron sputtering time is 70min to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Example 4: preparation of magnesium alloy surface super-hydrophobic composite film layer
(1) Grinding an AZ31 magnesium alloy sample by using 400#, 800#, 1500# abrasive paper in sequence, polishing, then placing into acetone, deionized water and absolute ethyl alcohol in sequence, cleaning for 3min by ultrasonic waves respectively, and drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, and vacuumizing until the vacuum degree is 5 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 250sccm, and carrying out sputtering cleaning on the Al target material and the Si target material for 5min;
after the sputtering cleaning of the target material is finished, regulating the air pressure of a vacuum chamber to be 1.5Pa, regulating the flow of argon gas to be 60sccm, combining with argon ion etching, and carrying out magnetron sputtering on the magnesium alloy with the surface treated with a layer of AlSi at the sputtering power of 150W and the room temperature;
wherein, the argon ion etching treatment comprises the following steps: firstly sputtering AlSi for 20min, then sputtering argon ions for 1min, then continuing sputtering AlSi for 20min, then sputtering argon ions for 1min, and repeating the steps for 10 times;
（3）opening a magnetron sputtering vacuum chamber, replacing two Al targets with Si targets with the purity of 99.99 percent, adjusting the distance between the target and the magnesium alloy sample with the surface attached with the AlSi layer prepared in the step (2) to be 100mm, and vacuumizing to be 5 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 250sccm, and carrying out sputtering cleaning on the Si target material for 5min;
after the sputtering and cleaning of the target material are finished, the air pressure of the vacuum chamber is adjusted to be 2.0Pa, the argon flow is 40sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 10:1, carrying out magnetron sputtering on a layer of SiO on the surface of the magnesium alloy sample with the AlSi film attached to the surface in the step (2) at room temperature and the sputtering power of 200W 2 And (3) performing film forming, wherein the magnetron sputtering time is 50min, and taking out a magnesium alloy sample to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Example 5: preparation of magnesium alloy surface super-hydrophobic composite film layer
(1) Sequentially grinding an AM60 magnesium alloy sample by using 400#, 800# and 1500# abrasive paper, polishing, sequentially putting the sample into acetone, deionized water and absolute ethyl alcohol, and ultrasonically cleaning for 10min, and blow-drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, and vacuumizing until the vacuum degree is 1 x 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 100sccm, and carrying out sputtering cleaning on the Al target material and the Si target material for 30min;
after the sputtering and cleaning of the target material are finished, adjusting the air pressure of a vacuum chamber to be 0.8Pa, adjusting the argon flow to be 30sccm, combining argon ion etching, and carrying out magnetron sputtering on the magnesium alloy with the surface treated by a layer of AlSi at the sputtering power of 30W and the room temperature;
wherein, the argon ion etching treatment comprises the following steps: firstly sputtering AlSi for 20min, then sputtering argon ions for 5min, then continuing to sputter AlSi for 20min, then sputtering argon ions for 5min, and repeating the steps for 5 times;
(3) Opening the magnetron sputtering vacuum chamber, replacing the two Al targets with Si targets with the purity of 99.99 percent, adjusting the target materials and the stepsThe distance between the magnesium alloy samples with the surface attached with the AlSi layer prepared in the step (2) is 100mm, and the magnesium alloy samples are vacuumized to be 1 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 100sccm, and carrying out sputtering cleaning on the Si target material for 30min;
after the sputtering cleaning of the target material is finished, the air pressure of the vacuum chamber is adjusted to be 0.7Pa, the argon flow is 20sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 5:1, carrying out magnetron sputtering on a layer of SiO on the surface of the magnesium alloy sample with the AlSi film attached to the surface in the step (2) at room temperature and the sputtering power of 40W 2 And (3) performing magnetron sputtering for 150min, and taking out the magnesium alloy sample to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Example 6: preparation of super-hydrophobic composite film layer on surface of magnesium alloy
(1) Sequentially grinding a WE43 magnesium alloy sample by using 400#, 800#, 1500# abrasive paper, polishing, sequentially putting into acetone, deionized water and absolute ethyl alcohol, respectively ultrasonically cleaning for 6min, and blow-drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, alternately putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and a magnesium alloy sample to be 80mm, and vacuumizing until the vacuum degree is 3 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 175sccm, and carrying out sputtering cleaning on the Al target material and the Si target material for 18min;
after the sputtering and cleaning of the target material are finished, regulating the air pressure of a vacuum chamber to be 1.1Pa, regulating the flow of argon to be 45sccm, combining with argon ion etching, and carrying out magnetron sputtering on the magnesium alloy with the surface treated by a layer of AlSi at the sputtering power of 90W and the room temperature;
wherein, the argon ion etching treatment comprises the following steps: sputtering AlSi for 15min, then sputtering argon ions for 3min, then continuing sputtering AlSi for 15min, then sputtering argon ions for 3min, and repeating the steps for 7 times;
(3) Opening a magnetron sputtering vacuum chamber, replacing the two Al targets with Si targets with the purity of 99.99%, adjusting the distance between the target and the magnesium alloy sample which is prepared in the step (2) and is provided with the AlSi layer on the surface to be 100mm, and vacuumizing to be3×10 -4 Pa, introducing argon with the purity of 99.999 percent, and carrying out sputtering cleaning on the Si target for 18min, wherein the flow of the argon is 175 sccm;
after the sputtering cleaning of the target material is finished, the air pressure of a vacuum chamber is adjusted to be 1.3Pa, the flow of argon is 30sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 7:1, carrying out magnetron sputtering on a layer of SiO on the surface of the magnesium alloy sample with the AlSi film attached to the surface in the step (2) at room temperature and the sputtering power of 120W 2 And (3) taking out a magnesium alloy sample after the magnetron sputtering time is 60min to obtain the magnesium alloy surface super-hydrophobic composite film layer.
Comparative example 1: preparation of MAO film on magnesium alloy surface by micro-arc oxidation method
(1) The method comprises the following steps of performing surface pretreatment on a magnesium alloy sample, sequentially grinding the magnesium alloy sample by 400#, 800# and 1500# abrasive paper, then performing polishing treatment, sequentially putting the magnesium alloy sample into acetone, deionized water and absolute ethyl alcohol, performing ultrasonic cleaning for 4min, and finally drying the magnesium alloy sample by blowing.
(2) And (3) immersing the magnesium alloy sample into an electrolyte consisting of 15g/L sodium silicate, 12g/L potassium fluoride, 3g/L sodium hydroxide and 10mL/L glycerol for treatment, wherein the power supply pulse frequency is 700Hz, the duty ratio is 25%, the voltage is 400V, and the MAO film layer on the surface of the magnesium alloy is obtained after the treatment for 20 min.
Comparative example 2: preparation of AlSi film layer on surface of magnesium alloy by magnetron sputtering
(1) Grinding an AZ91D magnesium alloy sample by using 400#, 800#, 1500# abrasive paper in sequence, polishing, then putting into acetone, deionized water and absolute ethyl alcohol in sequence, cleaning for 4min by ultrasonic waves respectively, and drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, putting two Al target materials with the purity of 99.99% and two Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, and vacuumizing until the vacuum degree is 2 multiplied by 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 130sccm, and carrying out sputtering cleaning on the Al target material and the Si target material for 20min;
after the sputtering and cleaning of the target material are finished, adjusting the air pressure of a vacuum chamber to be 1.0Pa, adjusting the flow of argon to be 35sccm, combining with argon ion etching, carrying out magnetron sputtering on the surface of the magnesium alloy with an AlSi layer at the sputtering power of 50W and the room temperature, and taking out a magnesium alloy sample to obtain an AlSi film on the surface of the magnesium alloy;
wherein, the argon ion etching treatment comprises the following steps: firstly sputtering AlSi for 15min, then sputtering argon ions for 3min, then continuing sputtering AlSi for 15min, then sputtering argon ions for 3min, and repeating the steps for 5 times.
Comparative example 3: preparation of SiO on magnesium alloy surface by magnetron sputtering 2 Film layer
(1) Sequentially grinding an AZ91D magnesium alloy sample by using 400#, 800# and 1500# abrasive paper, then polishing, sequentially putting into acetone, deionized water and absolute ethyl alcohol, respectively performing ultrasonic cleaning for 4min, and blow-drying for later use;
(2) Putting the magnesium alloy subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, putting Si target materials with the purity of 99.99% into four target positions, adjusting the distance between the target materials and the magnesium alloy sample subjected to surface pretreatment prepared in the step (1) to be 100mm, and vacuumizing to be 2 x 10 -4 Pa, introducing argon with the purity of 99.999 percent, wherein the flow of the argon is 130sccm, and carrying out sputtering cleaning on the Si target material for 20min;
after the sputtering cleaning of the target material is finished, the air pressure of the vacuum chamber is adjusted to be 1.0Pa, the argon flow is 40sccm, and meanwhile, oxygen with the purity of 99.999 percent is introduced, so that the flow ratio of the argon to the oxygen is ensured to be 6:1, carrying out magnetron sputtering on a layer of SiO on the surface of a magnesium alloy sample at room temperature and under the sputtering power of 80W 2 Film forming, magnetron sputtering time is 70min, and a magnesium alloy sample is taken out to obtain SiO on the surface of the magnesium alloy 2 And (3) a membrane.
Test example 1:
(1) The magnesium alloy surface super-hydrophobic composite membrane layer prepared in example 1 and the magnesium alloy surface MAO membrane prepared in comparative example 1 were structurally characterized by using a scanning electron microscope, as shown in FIG. 1.
As shown in FIG. 1, in comparative example 1, the surface of the MAO film layer on the surface of the magnesium alloy prepared by micro-arc oxidation has a plurality of pores and coarse microstructures, while the AlSi/SiO on the surface of the magnesium alloy prepared by the invention 2 The super-hydrophobic membrane layer has few surface pores and no thick microstructure, and is distributed with a large amount of SiO which is close to a circle 2 Microstructures having dimensions substantially in the range of a few hundred nanometers.
(2) The super-hydrophobic composite membrane layer on the surface of the magnesium alloy prepared in example 1 and the MAO membrane on the surface of the magnesium alloy prepared in comparative example 1 were measured by a three-dimensional profilometer, and the results are shown in fig. 2.
As can be seen from FIG. 2, the surface fluctuation degree of the film layer of the magnesium alloy surface film prepared by the micro-arc oxidation in the comparative example 1 is about + -10 um, compared with the AlSi/SiO on the magnesium alloy surface prepared by the invention 2 The surface fluctuation degree of the super-hydrophobic film layer is only about +/-4 um, and the surface roughness degree is obviously smaller.
Test example 2: testing the wettability of the surface of the film by water drops
The magnesium alloy prepared in the example 2 has the surface of AlSi/SiO 2 Super-hydrophobic film, MAO film on magnesium alloy surface prepared by micro-arc oxidation in comparative example 1, alSi film on magnesium alloy surface prepared in comparative example 2, and SiO film on magnesium alloy surface prepared in comparative example 3 2 The film was subjected to a surface water drop wettability test, and the results are shown in fig. 3.
The specific detection method comprises the following steps: measuring the wettability of water drops on the surface of the membrane layer by using a contact angle tester, fixing the sample on a sample table by using double faced adhesive tape, setting test parameters, dripping the water drops of 3 mu L on the surface of the test sample, and testing to obtain the contact angle of the test sample.
As can be seen from FIG. 3, the contact angle of the MAO film on the surface of the magnesium alloy prepared in comparative example 1 based on micro-arc oxidation was 49.6 deg., showing hydrophilic characteristics; the contact angle of the AlSi film on the surface of the magnesium alloy prepared by the comparative example 2 is 82.9 degrees, and the AlSi film has no hydrophobicity; comparative example 3 SiO on the surface of magnesium alloy 2 The contact angle of the film is 124.3 degrees, and the film shows certain hydrophobic property;
the AlSi/SiO prepared by the method 2 The contact angle of the film layer is obviously large and reaches 157.5 degrees, and the film layer has obvious super-hydrophobic property, and the analysis in combination with the figure 1 and the figure 2 shows that the film layer is just the large amount of nano-scale SiO on the surface of the composite film layer 2 The existence of the microstructure and the effect of smaller roughness of the surface of the film layer enable the prepared film layer to show obvious super-hydrophobic characteristics under the comprehensive influence.
Test example 3: corrosion resistance test
The magnesium alloy prepared in the example 2 has the surface of AlSi/SiO 2 Super-hydrophobic film, MAO film on magnesium alloy surface prepared based on micro-arc oxidation in comparative example 1, alSi film on magnesium alloy surface prepared in comparative example 2, and SiO film on magnesium alloy surface prepared in comparative example 3 2 The films were subjected to corrosion resistance tests, and the results are shown in table 1.
The specific detection method comprises the following steps: a potentiodynamic polarization method is adopted, a three-electrode system is adopted during testing, a testing solution is a NaCl water solution with the mass fraction of 3.5%, a saturated calomel electrode and a platinum electrode are respectively selected as a reference electrode and an auxiliary electrode, the scanning speed of the potential is set to be 1mV/s, the obtained polarization curve result is shown in figure 4, and the obtained polarization curve is subjected to fitting analysis by adopting a linear extrapolation method.
TABLE 1
| Group of | Corrosion potential/V | Corrosion current density/(A. Cm) -2 ) | Polarization resistance/(Ω · cm) 2 ) |
| Control group (magnesium alloy matrix) | -1.48 | 1.48×10 -5 | 1.40×10 3 |
| Example 2 (AlSi/SiO) 2 Composite film) | -1.24 | 6.76×10 -8 | 7.12×10 5 |
| COMPARATIVE EXAMPLE 1 (MAO Membrane) | -1.26 | 7.33×10 -7 | 7.50×10 4 |
| Comparative example 2 (AlSi film layer) | -1.31 | 2.45×10 -7 | 2.31×10 5 |
| Comparative example 3 (SiO) 2 Film layer) | -1.39 | 2.23×10 -5 | 3.06×10 3 |
According to the theory of electrochemistry correlation, the more positive the corrosion potential is, the smaller the thermodynamic possibility of corrosion, and the smaller the corrosion current density is, the larger the polarization resistance is, the smaller the kinetic possibility of corrosion is, indicating the better corrosion resistance of the material. As can be seen from FIG. 4 and Table 1, in comparison with the magnesium alloy substrate, the magnesium alloy MAO film prepared in comparative example 1 based on micro-arc oxidation, the AlSi film layer obtained in comparative example 2 by magnetron sputtering, and the SiO film layer obtained in comparative example 3 by magnetron sputtering 2 Film layer and AlSi/SiO on surface of magnesium alloy prepared by the invention 2 The super-hydrophobic composite film layers enable the corrosion potential to be shifted positively, the corrosion current density to be reduced, and meanwhile, the polarization resistance to be increased, which shows that the corrosion resistance of the magnesium alloy matrix is increased by the four film layers.
As can be seen by further comparing the four membrane layers, the surface AlSi/SiO of the magnesium alloy obtained by the invention is compared with the MAO membrane layer obtained in the comparative example 1 and the AlSi membrane layer obtained in the comparative example 2 which have no hydrophobic property 2 Super-hydrophobic composite membraneThe layer enables the reduction degree of the corrosion current density to be larger, the corrosion current density is reduced by more than 1 order of magnitude, simultaneously, the polarization resistance is increased by more than 1 order of magnitude and more than 2 times, which shows that the AlSi/SiO on the surface of the magnesium alloy prepared by the invention 2 Due to the excellent super-hydrophobicity of the super-hydrophobic composite film layer, the corrosion resistance of the magnesium alloy is obviously improved; and the SiO obtained in comparative example 3 with certain hydrophobic property 2 Compared with the film, the composite film obtained by the invention has more obvious corrosion resistance advantage, the reduction degree of the corrosion current density reaches 3 orders of magnitude, and the polarization resistance is increased by 2 orders of magnitude, because the SiO obtained by the comparative example 3 2 Although the film has certain hydrophobic property, the corrosion medium is easier to penetrate SiO due to the lack of the synergistic effect of the AlSi film layer 2 The film reaches the magnesium alloy matrix, so the corrosion resistance of the film is greatly improved, which more fully embodies the AlSi/SiO obtained by the invention 2 The performance advantage of the composite film layer.
In conclusion, the invention provides a method for preparing a super-hydrophobic composite film layer on the surface of a magnesium alloy. The prepared film layer has nano-scale microstructures and smaller surface roughness on the surface, and the super-hydrophobic property is very excellent.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a magnesium alloy surface super-hydrophobic composite film layer is characterized by comprising the following steps: (1) carrying out surface pretreatment on a magnesium alloy sample;
(2) Sputtering an AlSi layer on the magnesium alloy sample subjected to surface pretreatment obtained in the step (1) by adopting an Al target and an Si target;
(3) Replacing the Al target with a Si target, and sputtering SiO on the magnesium alloy sample with the AlSi layer attached to the surface in the step (2) 2 Taking out a magnesium alloy sample to obtain the magnesium alloy surfaceAnd (3) coating a super-hydrophobic composite film layer.
2. The method for preparing the magnesium alloy surface superhydrophobic composite film layer according to claim 1, wherein in the step (1), the magnesium alloy is one of AZ31, AM60, AZ91D or WE 43;
the method for pretreating the surface of the magnesium alloy sample comprises the following steps: and sequentially grinding the magnesium alloy sample by using 400#, 800# and 1500# abrasive paper, polishing, sequentially putting into acetone, deionized water and absolute ethyl alcohol, ultrasonically cleaning for 3-10 min, and drying.
3. The preparation method of the magnesium alloy surface superhydrophobic composite film according to claim 1, wherein the purity of the Al target and the Si target is not less than 99.99%.
4. The preparation method of the magnesium alloy surface superhydrophobic composite film layer according to claim 1, wherein in the step (2), the method for sputtering the AlSi layer comprises the following steps: and (2) putting the magnesium alloy sample subjected to surface pretreatment in the step (1) into a magnetron sputtering vacuum chamber, alternately putting two Al target materials and two Si target materials into four target positions, adjusting the distance between the target materials and the magnesium alloy sample to be 80mm, vacuumizing, introducing argon, carrying out sputtering cleaning on the target materials, adjusting the flow of the argon and the air pressure of the vacuum chamber after the sputtering cleaning of the target materials is finished, combining argon ion etching, and sputtering an AlSi layer on the surface of the magnesium alloy sample.
5. The preparation method of the magnesium alloy surface superhydrophobic composite film layer according to claim 4, wherein the argon purity is more than or equal to 99.999%;
the sputtering and cleaning parameters of the target are as follows: degree of vacuum 1X 10 -4 ~5×10 -4 Pa, the argon flow is 100 to 250sccm, and the sputtering cleaning time is 5 to 30min;
the parameters of the sputtered AlSi layer are as follows: the argon flow is 30 to 60sccm, the vacuum chamber pressure is 0.8 to 1.5Pa, the sputtering power is 30 to 150W, and the sputtering temperature is room temperature.
6. The preparation method of the magnesium alloy surface superhydrophobic composite film layer according to claim 4, wherein the argon ion etching is performed by: sputtering AlSi for 10-20min, then sputtering argon ions for 1-5min, then continuously sputtering AlSi for 10-20min, then sputtering argon ions for 1-5min, and repeating the steps for 5-10 times.
7. The preparation method of the magnesium alloy surface superhydrophobic composite film layer according to claim 1, wherein in the step (3), siO is sputtered 2 The method of the layer is as follows: adjusting the distance between the target and the magnesium alloy sample with the AlSi layer on the surface prepared in the step (2) to be 100mm, vacuumizing, introducing argon, carrying out sputtering cleaning on the target, adjusting the flow and the pressure of the vacuum chamber after the sputtering cleaning of the target is finished, simultaneously introducing oxygen, and sputtering SiO on the surface of the magnesium alloy sample with the AlSi layer on the surface prepared in the step (2) 2 A layer.
8. The preparation method of the magnesium alloy surface superhydrophobic composite film layer according to claim 7, wherein the purity of argon is more than or equal to 99.999 percent, and the purity of oxygen is more than or equal to 99.999 percent;
the sputtering and cleaning parameters of the target are as follows: degree of vacuum 1X 10 -4 ~5×10 -4 Pa, the argon flow is 100 to 250sccm, and the sputtering cleaning time is 5 to 30min;
sputtering of SiO 2 The parameters of the layers are: argon flow rate of 20 to 40sccm, flow rate ratio of argon to oxygen (5 to 10): 1, the air pressure of a vacuum chamber is 0.7 to 2.0Pa, the sputtering power is 40 to 200W, the sputtering temperature is room temperature, and the sputtering time is 50 to 150min.
9. The magnesium alloy surface super-hydrophobic composite film layer prepared by the preparation method of any one of claims 1 to 8.
10. The magnesium alloy surface superhydrophobic composite film layer according to claim 9, wherein the magnesium alloy surface superhydrophobic composite film layer comprises an AlSi layer and an SiO layer in sequence from inside to outside 2 A layer;
the wetting contact angle of the super-hydrophobic composite film layer on the surface of the magnesium alloy is 157.5 degrees.
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