Ceramic film layer on surface of copper alloy as well as preparation method and application of ceramic film layer

Abstract

The invention belongs to the field of material surface treatment and ocean engineering, and particularly relates to a ceramic film layer on the surface of a copper alloy and a preparation method and application of the ceramic film layer. The preparation method comprises the steps that copper or a copper alloy serves as an anode, an inert electrode serves as a cathode, a metaaluminate-containing solution serves as electrolyte, micro-arc oxidation is conducted while ultrasonic treatment is conducted on the electrolyte, and a ceramic-metal composite film layer is formed on the surface of the copper or the copper alloy; the temperature of the electrolyte is 0-20 DEG C; and the maximum voltage of micro-arc oxidation is limited to be 600V. According to the method, the temperature of the electrolyte is controlled, the electrolyte is subjected to ultrasonic treatment, meanwhile, the highest voltage of micro-arc oxidation is limited, the ceramic-metal composite film layer with high density is generated on the surface of the anode in situ, and the composite film layer contains a large number of spherical metal copper nanoparticles. The obtained composite film layer has excellent corrosion resistance, can effectively inhibit biological fouling, and is especially suitable for aluminum bronze parts needing to be in direct contact with seawater for a long time.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of material surface treatment and marine engineering, and particularly relates to a ceramic film layer on a copper alloy surface and a preparation method and application thereof. BACKGROUND

[0002] Aluminum bronze alloy has excellent electrical conductivity, thermal conductivity, good mechanical properties and processing formability, and can inhibit the growth of marine organisms, and is therefore widely used in marine engineering. Aluminum bronze alloy is mainly used for military ships and marine transport vessels (including aircraft carriers, cruisers, destroyers, submarines, etc.), as key components such as propellers, power supply systems, heat exchange devices, etc.

[0003] Aluminum bronze alloy components need to be in direct contact with seawater for a long time, such as shaft propulsion system rotors, stator outer sheaths, cover plates and other components. In order to ensure stable service in seawater environment, aluminum bronze alloy needs to have excellent corrosion resistance and antifouling performance to inhibit corrosion thinning and perforation of aluminum bronze alloy and attachment and growth of marine organisms.

[0004] Generally speaking, copper alloy has good antifouling ability: when copper alloy is in direct contact with seawater, it will continuously release copper ions, and copper ions have a significant growth inhibitory effect on marine organisms. Generally, the daily Cu release per unit area reaches 10 μg / cm 2 However, whether based on surface treatment or alloying strategy optimization, the improvement of the corrosion resistance of copper alloy will inevitably affect the release of Cu (the higher the corrosion resistance, the more inhibited the release of copper ions). In other words, there is an irreconcilable contradiction between the corrosion resistance and the antifouling performance of copper alloy, and at present, the service life of copper alloy is mainly sacrificed (the corrosion resistance is reduced) to ensure the antifouling performance.

[0005] Micro-arc oxidation (MAO), also known as plasma electrolytic oxidation (PEO), is a common electrochemical surface treatment method for valve metals (such as Al). For copper and its alloys, as typical non-valve metals, a passivation film can be deposited on the surface to achieve stable plasma discharge, so as to obtain a micro-arc oxidation film layer on the copper surface to improve its corrosion resistance. However, the micro-arc oxidation film layer obtained by the above method greatly inhibits the dissolution of the copper matrix, resulting in a significant reduction in the release of copper ions, thereby reducing the antifouling performance, which is difficult to meet the needs of copper alloy components exposed to marine environment for a long time to inhibit the effect of biological fouling. SUMMARY

[0006] Therefore, the present application aims to provide a ceramic-metal composite film layer on the surface of copper or copper alloy and a preparation method and application thereof.

[0007] The present application provides a preparation method of a ceramic-metal composite film layer on the surface of copper or copper alloy, comprising the following steps:

[0008] The ceramic-metal composite film layer on the surface of copper or copper alloy is formed by micro-arc oxidation of copper or copper alloy as an anode, inert electrode as a cathode and metaborate-containing solution as electrolyte, while the electrolyte is ultrasonically treated.

[0009] The temperature of the electrolyte is 0-20℃, and the highest voltage limit of the micro-arc oxidation is 600V.

[0010] Preferably, the concentration of metaborate in the metaborate-containing solution is 0.02-0.2mol / L.

[0011] Preferably, the solutes in the metaborate-containing solution further include one or more of sodium silicate, sodium hydroxide and potassium dihydrogen phosphate.

[0012] Preferably, the temperature of the electrolyte is 7-18℃.

[0013] Preferably, the highest voltage limit of the micro-arc oxidation is 400-600V.

[0014] Preferably, the power of the ultrasonic treatment is 50-800W, and the frequency is 20-50kHz.

[0015] Preferably, the current density of the micro-arc oxidation is 0.02-1.00A / cm 2 , the working frequency is 100-2000Hz, the duty cycle is 5%-70%, and the treatment time is 5-30min.

[0016] Preferably, the material of the inert electrode is platinum, graphite or stainless steel, and the distance between the anode and the cathode is 3-20cm.

[0017] The present application further provides copper or copper alloy with the ceramic-metal composite film layer on the surface prepared by the above-mentioned preparation method, wherein the ceramic-metal composite film layer contains copper nanoparticles.

[0018] The present application further provides the application of the copper or copper alloy with the ceramic-metal composite film layer on the surface in the field of marine engineering.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] The application provides a preparation method of a ceramic-metal composite film layer on a copper or copper alloy surface, comprising the following steps: taking copper or copper alloy as an anode, taking an inert electrode as a cathode, taking a solution containing meta-aluminates as an electrolyte, and performing micro-arc oxidation while performing ultrasonic treatment on the electrolyte, so that a ceramic-metal composite film layer is formed on the copper or copper alloy surface; the temperature of the electrolyte is 0-20 DEG C; and the highest voltage limit of the micro-arc oxidation is 600 V.

[0021] The application adopts a one-step micro-arc oxidation method to construct a composite structure on the copper or copper alloy surface: a ceramic-metal (copper) composite film layer with few defects, high density and tight combination with the substrate is grown on the substrate, and corrosion protection of the copper or copper alloy substrate is realized by means of the high physical isolation effect; meanwhile, the molten copper is more prone to quenching effect by using a low-temperature electrolyte (0-20 DEG C), the copper is prevented from being oxidized too fast by limiting the voltage (the highest voltage limit is 600 V), the mass transfer process of the electrolyte is accelerated and the oxidation of the copper is reduced by means of ultrasonic auxiliary means, a large number of copper-rich nanoparticles are retained in the micro-arc oxidation ceramic-metal composite film layer, the continuous dissolution of copper ions is ensured based on the dissolution of the copper-rich nanoparticles, and the composite film layer can effectively inhibit the attachment and reproduction of marine organisms.

[0022] The micro-arc oxidation ceramic-metal composite film layer prepared by the preparation method has high hardness, high wear resistance, high corrosion resistance and antifouling ability, is simple and convenient to operate, has low requirements on equipment, and is conducive to industrialized mass production.

[0023] The micro-arc oxidation film layer with good corrosion resistance and antifouling performance can be prepared by only one micro-arc oxidation process, the aluminum bronze parts which need to be directly contacted with seawater for a long time can be applied, the marine corrosion resistance and antifouling performance are significantly improved, the service life is prolonged, and the related structure design (without the need of designing corrosion protection devices or antifouling devices) and maintenance procedures can be simplified. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description only constitute some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0025] Figure 1 SEM photos of the surfaces of the ceramic-metal composite film layers prepared for Example 1;

[0026] Figure 2EDX composition distribution map of the surface of the ceramic-metal composite film layer prepared in Example 1;

[0027] Figure 3 SEM photo of the cross section of the ceramic-metal composite film layer prepared in Example 1;

[0028] Figure 4 EDX composition distribution map of the cross section of the ceramic-metal composite film layer prepared in Example 1;

[0029] Figure 5 High-resolution TEM result of the nanoparticles in the ceramic-metal composite film layer prepared in Example 1;

[0030] Figure 6 Comparison result of the average copper ion release rate of the ceramic-metal composite film layers prepared in Example 1 and Comparative Examples 1-2;

[0031] Figure 7 Comparison result of the 0.01 Hz electrochemical impedance of the ceramic-metal composite film layers prepared in Example 1 and Comparative Examples 1-2;

[0032] Figure 8 Comparison result of the average copper ion release rate of the ceramic-metal composite film layers prepared in Example 2 and Comparative Examples 3-4;

[0033] Figure 9 Comparison result of the 0.01 Hz electrochemical impedance of the ceramic-metal composite film layers prepared in Example 2 and Comparative Examples 3-4;

[0034] Figure 10 Comparison result of the average copper ion release rate of the ceramic-metal composite film layers prepared in Example 3 and Comparative Examples 5-8;

[0035] Figure 11 Comparison result of the 0.01 Hz electrochemical impedance of the ceramic-metal composite film layers prepared in Example 3 and Comparative Examples 5-8;

[0036] Figure 12 Schematic diagram of the ceramic-metal composite film layer of the present application exerting the anti-fouling, wear-resistant and corrosion-resistant performance. DETAILED DESCRIPTION

[0037] The present application provides a preparation method of a ceramic-metal composite film layer on the surface of copper or copper alloy, comprising the following steps:

[0038] Taking copper or copper alloy as an anode, taking an inert electrode as a cathode, taking a metavanadate-containing solution as an electrolyte, and performing micro-arc oxidation while performing ultrasonic treatment on the electrolyte, so that a ceramic-metal composite film layer is formed on the surface of copper or copper alloy;

[0039] The temperature of the electrolyte is 0-20℃; the maximum voltage of the micro-arc oxidation is limited to 600V.

[0040] In the present application, the materials and equipment used are commercially available goods in the art, unless otherwise specified.

[0041] In the present application, the copper alloy is preferably an aluminum bronze alloy, which preferably comprises one or more of QAl9-2, QAl14-8-3-2, QAl9-4-4-2, QAl9-4, QAl7 and QAl10-4-4, and is a copper-based alloy with aluminum as the main alloying element.

[0042] In the present application, the copper or copper alloy preferably further comprises the following steps before use: oil and dirt removal treatment, polishing, cleaning and drying. The polishing preferably comprises polishing with 200#, 600#, 800# and 2000# sandpaper in sequence; the cleaning preferably comprises using acetone.

[0043] In the present application, the material of the inert electrode is preferably platinum, graphite or stainless steel, and the inert electrode can be a platinum sheet or a stainless steel sheet.

[0044] In the present application, the distance between the anode and the cathode is preferably 3-20cm, and can be 6cm or 12cm.

[0045] In the present application, the concentration of the meta-aluminates in the meta-aluminate-containing solution (electrolyte solution) is preferably 0.02-0.2mol / L, and can be 0.098mol / L, 0.1mol / L or 0.12mol / L. The meta-aluminates can passivate the surface of the material, and the concentration of the meta-aluminates in the present application has strong passivation effect on the surface of the copper or copper alloy and is conducive to the growth of the film layer. The meta-aluminate-containing solution is a uniform solution system with meta-aluminates as the main body. The meta-aluminates in the meta-aluminate-containing solution are preferably sodium meta-aluminate, and the concentration of the sodium meta-aluminate can be 8g / L, 8.5g / L or 10g / L.

[0046] In the present application, the solute in the meta-aluminic acid salt containing solution preferably further comprises one or more of sodium silicate, sodium hydroxide and potassium dihydrogen phosphate. The sodium silicate can passivate the surface, the sodium hydroxide and the potassium dihydrogen phosphate can adjust the pH value of the electrolyte, the potassium dihydrogen phosphate can also densify the film layer and regulate the growth kinetics. The concentration of the sodium silicate in the meta-aluminic acid salt containing solution is preferably 2-30 g / L, specifically 3.6 g / L, 5 g / L or 22 g / L, the concentration of the sodium hydroxide is preferably 0-5 g / L, specifically 0.8 g / L, and the concentration of the potassium dihydrogen phosphate is preferably 0-5 g / L, specifically 2.7 g / L. The meta-aluminic acid salt containing solution specifically can comprise 8 g / L of sodium meta-aluminate and 5 g / L of sodium silicate, or 10 g / L of sodium meta-aluminate, 22 g / L of sodium silicate and 0.8 g / L of sodium hydroxide, or 8.5 g / L of sodium meta-aluminate, 3.6 g / L of sodium silicate and 2.7 g / L of potassium dihydrogen phosphate.

[0047] In the present application, the power of the ultrasonic treatment is preferably 50-800 W, specifically 360 W, 500 W or 600 W, and the frequency is preferably 20-50 kHz, specifically 40 kHz or 50 kHz. The ultrasonic treatment condition in the present application can maintain the surface passivation. The present application can not only accelerate the electrolyte mass transfer process, promote the deposition and growth of the passivation layer, and provide the basis for the plasma discharge process, but also promote the increase of the plasma discharge position and reduce the average energy density of the plasma discharge, reduce the oxidation of the copper, and at the same time, the ultrasonic field can increase the fluidity of the molten copper, and promote the copper in the ceramic-metal composite film layer to exist in the form of small and uniform nanoparticles.

[0048] In the present application, the temperature of the electrolyte is preferably 7-18℃, specifically 10±3℃ or 15±3℃. The present application can ensure the low-temperature characteristics of the electrolyte, so that the molten copper is more prone to quenching effect, and the chemical oxidation rate is also weakened, so that the copper particles can be retained in the obtained micro-arc oxidation ceramic-metal composite film layer.

[0049] In the present application, the maximum voltage of the micro-arc oxidation is preferably limited to 400-600 V, specifically 450 V, 500 V or 600 V. The present application can limit the maximum value of the micro-arc oxidation voltage, prevent the copper from being oxidized too fast, and inhibit the gasification of the copper under the premise of ensuring the growth rate of the ceramic-metal composite film layer.

[0050] In the present application, the current density of the micro-arc oxidation is preferably 0.02-1.00 A / cm 2 , specifically 0.10 A / cm 2 , 0.2 A / cm 2 or 1.00 A / cm2 The working frequency is preferably 100-2000 Hz, and can be 800 Hz, 1000 Hz or 2000 Hz; the duty cycle is preferably 5%-70%, and can be 5% or 10%; the processing time is preferably 5-30 min, and can be 10 min or 20 min. In the micro-arc oxidation process, the local high temperature caused by plasma discharge promotes the melting of the copper alloy substrate in the region. However, the molten copper is not stable in the environment and is easily oxidized to form a ceramic film layer. In the micro-arc oxidation process of the present application, the low temperature characteristics of the electrolyte are ensured, the highest voltage is limited, and ultrasonic assistance is performed, so that the copper nanoparticles with uniform distribution and small particle size are retained in the obtained micro-arc oxidation ceramic-metal composite film layer.

[0051] In the present application, the copper or copper alloy with the ceramic-metal composite film layer on the surface preferably further comprises washing and drying after the micro-arc oxidation; the washing is preferably water rinsing, and the drying is preferably natural air drying.

[0052] In the present application, the metaborate system with strong surface passivation is used as the micro-arc oxidation electrolyte, and the temperature of the electrolyte is effectively controlled during the micro-arc oxidation process, and the electrolyte is subjected to ultrasonic treatment; the copper or copper alloy is used as the micro-arc oxidation anode, and the inert electrode is used as the cathode for micro-arc oxidation; the highest voltage that can be reached is set to limit the voltage during the micro-arc oxidation process; the problem of poor antifouling performance of the aluminum bronze alloy micro-arc oxidation film layer in the prior art is solved,

[0053] The present application also provides a copper or copper alloy with a ceramic-metal composite film layer on the surface obtained by the preparation method of the above technical solution, and the ceramic-metal composite film layer contains copper nanoparticles.

[0054] In the present application, the thickness of the ceramic-metal composite film layer is preferably 20-500 μm. The ceramic-metal composite film layer obtained by the present application has high density, and the density is 2%-10%.

[0055] The present application also provides the application of the copper or copper alloy with a ceramic-metal composite film layer on the surface in the field of marine engineering.

[0056] The copper alloy with a ceramic-metal composite film layer obtained by the present application can be used as an aluminum bronze part that needs to be in direct contact with seawater for a long time, which can significantly improve the marine corrosion resistance and effectively inhibit the growth of marine organisms.

[0057] The application provides a micro-arc oxidation method based on voltage limitation, low-temperature electrolyte and ultrasonic assistance, which ensures that the micro-arc oxidation film layer on the surface of copper or copper alloy has high corrosion resistance and high antifouling capacity, and is beneficial to the large-scale industrial application of micro-arc oxidation on marine aluminum bronze alloy. The application obtains a high-density micro-arc oxidation ceramic-metal composite film layer to ensure its corrosion resistance by limiting the highest voltage in the micro-arc oxidation process (metal copper is retained without being oxidized), controlling the electrolyte temperature (low temperature inhibits the growth of metal copper) and adding ultrasonic assistance (breaks copper particles), while retaining metal copper nanoparticles in the micro-arc oxidation ceramic-metal composite film layer, and ensuring the antifouling characteristics of the film layer through the controllable release of the metal copper nanoparticles, so that the corrosion resistance and antifouling performance of the film layer are effectively improved.

[0058] In order to further illustrate the application, the ceramic-metal composite film layer on the surface of copper or copper alloy and the preparation method and application thereof provided by the application are described in detail below with reference to the drawings and examples, but they should not be understood as limiting the protection scope of the application.

[0059] Example 1

[0060] (1) The QAl9-2-Y aluminum bronze alloy was subjected to oil and dirt removal treatment (acetone), and then was polished by using 200#, 600#, 800# and 2000# sandpaper in sequence, and was washed with acetone and dried; the sample was wrapped with insulating tape to ensure that the reaction area had a size of 20 mm*20 mm, and the pretreated QAl9-2-Y aluminum bronze alloy was obtained.

[0061] (2) A micro-arc oxidation solution was prepared, which contained 8 g / L sodium metaaluminate and 5 g / L sodium silicate; the solution was fully stirred by using a magnetic stirrer to ensure uniform dispersion, and was used as an electrolyte;

[0062] (3) The pretreated QAl9-2-Y aluminum bronze alloy was used as an anode, and stainless steel was used as a cathode; the anode and the cathode were connected to a pulse power supply, the distance between the anode and the cathode plates was 6 cm, and they were placed in the above-mentioned electrolyte; an ultrasonic field with a power of 360 W and a frequency of 40 kHz was used to assist the micro-arc oxidation process; the micro-arc oxidation power supply parameters were set as follows: the current density was 0.2 A / cm 2 , the highest voltage was limited to 600 V, the frequency was 2000 Hz, the total duty cycle was 5%, the electrolyte temperature was 10±3℃, and the time was 600 s;

[0063] (4) After the micro-arc oxidation reaction was completed, the anode sample with the ceramic-metal composite film layer was washed with deionized water and was naturally dried, and the micro-arc oxidation ceramic-metal composite film layer was obtained on the surface of the QAl9-2-Y aluminum bronze alloy.

[0064] Comparative Example 1

[0065] The difference from Example 1 is only that no voltage limiting is performed (no maximum voltage is set), and the rest of the steps and conditions are the same.

[0066] Comparative Example 2

[0067] The difference from Example 1 is only that no ultrasonic assistance is performed, and the rest of the steps and conditions are the same.

[0068] Example 2

[0069] (1) The QAl10-4-4 aluminum bronze alloy was subjected to degreasing and decontamination treatment, and then was polished step by step using sandpaper, washed with acetone and dried; the sample was wrapped with insulating tape to ensure that the reaction area was 10 mm x 10 mm in size, to obtain the pretreated QAl10-4-4 aluminum bronze alloy;

[0070] (2) A micro-arc oxidation solution was prepared, containing 10 g / L sodium metaaluminate, 22 g / L sodium silicate and 0.8 g / L sodium hydroxide; the solution was stirred well by a magnetic stirrer to ensure uniform dispersion, and was used as the electrolyte;

[0071] (3) The pretreated QAl10-4-4 aluminum bronze alloy was used as the anode, and stainless steel was used as the cathode; the anode and the cathode were connected to a pulse power supply, and the distance between the anode and the cathode was 12 cm; the micro-arc oxidation process was assisted by an ultrasonic field with a power of 500 W and a frequency of 50 kHz; the micro-arc oxidation power supply parameters were set as follows: the current density was 0.10 A / cm 2 , the maximum voltage limit was 500 V, the frequency was 1000 Hz, the total duty cycle was 10%, the electrolyte temperature was 15±3℃, and the time was 600 s;

[0072] (4) After the micro-arc oxidation reaction was completed, the anode sample with the ceramic-metal composite film layer was washed with deionized water and naturally air-dried, to obtain the micro-arc oxidation ceramic-metal composite film layer on the surface of the QAl10-4-4 aluminum bronze alloy.

[0073] Comparative Example 3

[0074] The difference from Example 2 is only that no voltage limiting is performed, and the rest of the steps and conditions are the same.

[0075] Comparative Example 4

[0076] The difference from Example 2 is only that no electrolyte temperature control is performed, and the rest of the steps and conditions are the same.

[0077] Example 3

[0078] (1) The QAl14-8-3-2 aluminum bronze alloy was subjected to degreasing and decontamination treatment, and then was polished step by step with sandpaper, washed with acetone and dried; the sample was wrapped with insulating tape to ensure that the reaction area was 15 mm x 15 mm in size, to obtain the pretreated QAl14-8-3-2 aluminum bronze alloy;

[0079] (2) A micro-arc oxidation solution was prepared, containing 8.5 g / L sodium metaaluminate, 3.6 g / L sodium silicate and 2.7 g / L potassium dihydrogen phosphate; the solution was stirred by a magnetic stirrer to make it uniformly dispersed, serving as the electrolyte;

[0080] (3) The pretreated QAl14-8-3-2 aluminum bronze alloy was used as the anode, and stainless steel was used as the cathode; the anode and the cathode were connected to a pulse power supply, and the distance between the anode and the cathode plates was 12 cm, and they were placed in the above-mentioned electrolyte; an ultrasonic field with a power of 600 W and a frequency of 50 kHz was used to assist the micro-arc oxidation process; the micro-arc oxidation power supply parameters were set as follows: the current density was 1.00 A / cm 2 , the maximum voltage limit was 450 V, the frequency was 800 Hz, the total duty cycle was 10%, the electrolyte temperature was 10±3℃, and the time was 1200 s;

[0081] (4) After the micro-arc oxidation reaction was completed, the anode sample with the ceramic-metal composite film layer was taken out and washed with deionized water, and then was naturally dried, to obtain the micro-arc oxidation ceramic-metal composite film layer on the surface of the QAl14-8-3-2 aluminum bronze alloy.

[0082] Comparative Example 5

[0083] The difference from Example 3 is only that the voltage limiting is not performed, and the rest of the steps and conditions are the same.

[0084] Comparative Example 6

[0085] The difference from Example 3 is only that the electrolyte temperature control is not performed, and the rest of the steps and conditions are the same.

[0086] Comparative Example 7

[0087] The difference from Example 3 is only that the ultrasonic assistance is not performed, and the rest of the steps and conditions are the same.

[0088] Comparative Example 8

[0089] The difference from Example 3 is only that sodium metaaluminate is not added to the electrolyte, and the rest of the steps and conditions are the same. Almost no film layer grows on the surface of the aluminum bronze alloy, and the performance is similar to that of the bare substrate.

[0090] Figure 1The SEM photo of the surface of the ceramic-metal composite film layer prepared in Example 1 shows that the obtained micro-arc oxidation ceramic-metal composite film layer has a porous feature and a large number of granular features.

[0091] Figure 2 The EDX composition distribution map of the surface of the ceramic-metal composite film layer prepared in Example 1 shows that the granular features on the surface of the micro-arc oxidation ceramic-metal composite film layer are copper-rich particles.

[0092] Figure 3 The SEM photo of the cross section of the ceramic-metal composite film layer prepared in Example 1 shows that the micro-arc oxidation ceramic-metal composite film layer has few defects and is tightly combined with the substrate, and a large number of granular features appear in the cross section.

[0093] Figure 4 The EDX composition distribution map of the cross section of the ceramic-metal composite film layer prepared in Example 1 shows that the granular features on the surface of the micro-arc oxidation ceramic-metal composite film layer are copper-rich particles.

[0094] Figure 5 The high-resolution TEM result of the copper-rich particles in the ceramic-metal composite film layer prepared in Example 1 confirms that most of the copper-rich nanoparticles in the ceramic-metal composite film layer are metal copper particles and also have cuprous oxide particles.

[0095] Figure 6 The average copper ion release rate result of the ceramic-metal composite film layer prepared in Example 1 (indicated as Example 1 in the figure) and the state of no pressure limitation (Comparative Example 1) and no ultrasonic assistance (Comparative Example 2) shows that the copper ion release rate of the preparation method of the present application is much higher than that of other cases, reaching 17 μg / cm 2 .

[0096] Figure 7 The 0.01 Hz electrochemical impedance result of the ceramic-metal composite film layer prepared in Example 1 and the state of no pressure limitation and no ultrasonic assistance shows that the preparation method of the present application does not significantly affect the corrosion resistance of the film layer.

[0097] Figure 8 The average copper ion release rate result of the ceramic-metal composite film layer prepared in Example 2 and the state of no pressure limitation (Comparative Example 3) and no temperature control (Comparative Example 4) shows that the copper ion release rate of the preparation method of the present application is much higher than that of other cases, reaching 12.2 μg / cm 2 .

[0098] Figure 9The 0.01Hz electrochemical impedance results of the ceramic-metal composite film layer prepared in Example 2 are shown in Table 2, and the results of the state without pressure limitation and without temperature control are used as a comparison, which shows that the preparation method of the application does not significantly affect the corrosion resistance of the film layer.

[0099] Figure 10 The average copper ion release rate results of the ceramic-metal composite film layer prepared in Example 3 are shown in Table 3, and the results of the state without pressure limitation (Comparative Example 5), without temperature control (Comparative Example 6), without ultrasonic assistance (Comparative Example 7), and without the addition of metallasilate (Comparative Example 8) are used as a comparison, which shows that the copper ion release rate of the preparation method of the application is much higher than that of other cases, which is 15.4ug / cm 2 .

[0100] Figure 11 The 0.01Hz electrochemical impedance results of the ceramic-metal composite film layer prepared in Example 3 are shown in Table 2, and the results of the state without pressure limitation and without temperature control are used as a comparison, which shows that the preparation method of the application does not significantly affect the corrosion resistance of the film layer.

[0101] Figure 12 A schematic diagram of the ceramic-metal composite film layer of the application to play the anti-fouling, wear-resistant and corrosion-resistant performance.

[0102] The composite film layer prepared by the preparation method of the application has strong bonding force with the substrate, which can reach 10.6N. The composite film layer of the application can enhance the corrosion resistance and anti-fouling performance of the aluminum bronze alloy surface. The application uses voltage limitation, low-temperature electrolyte, and ultrasonic-assisted micro-arc oxidation to prepare a ceramic-metal composite film layer on the surface of aluminum bronze, which can prepare a ceramic-metal composite film layer with corrosion resistance and anti-fouling performance on the surface of aluminum bronze alloy. It can be used as a surface treatment method for copper alloy for marine engineering, and is suitable for aluminum bronze alloy materials for marine engineering that need to be in direct contact with seawater for a long time.

[0103] Although the above examples have made a detailed description of the application, it is only a part of the embodiments of the application, not all the embodiments, and other embodiments can be obtained according to the embodiments of the application without creative labor, which are within the protection scope of the application.

Claims

1. A method for producing a ceramic-metal composite film layer on a copper or copper alloy surface, characterized by, The method comprises the following steps: a ceramic-metal composite film layer is formed on the surface of the copper or copper alloy by micro-arc oxidation with a copper or copper alloy as an anode, an inert electrode as a cathode, and a metatungstate-containing solution as an electrolyte, while the electrolyte is ultrasonically treated; the temperature of the electrolyte is 0-20℃; and the highest voltage limit of the micro-arc oxidation is 600V.

2. The production method according to claim 1, characterized by, the concentration of the metatungstate in the metatungstate-containing solution is 0.02-0.2mol / L.

3. The production method according to claim 1 or 2, characterized by, the solutes in the metatungstate-containing solution further include one or more of sodium silicate, sodium hydroxide and potassium dihydrogen phosphate.

4. The method of claim 1, wherein, the temperature of the electrolyte is 7-18℃.

5. The preparation method according to claim 1, characterized in that, the highest voltage limit of the micro-arc oxidation is 400-600V.

6. The method of claim 1, wherein, the power of the ultrasonic treatment is 50-800W, and the frequency is 20-50kHz.

7. The production method according to claim 1 or 6, characterized by, The current density of the micro-arc oxidation is 0.02-1.00 A / cm 2 The working frequency is 100-2000 Hz, the duty cycle is 5%-70%, and the processing time is 5-30 min.

8. The method of claim 1, wherein, the material of the inert electrode is platinum, graphite or stainless steel; and the distance between the anode and the cathode is 3-20cm.

9. The copper or copper alloy having a ceramic-metal composite film layer on the surface, obtained by the production method according to any one of claims 1 to 8, characterized in that, the ceramic-metal composite film layer contains copper nanoparticles.

10. The application of the copper or copper alloy with the ceramic-metal composite film layer in the field of marine engineering according to claim 9.

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