Wear-resistant and antifouling propeller and preparation method thereof

Abstract

The application provides a wear-resistant and antifouling propeller and a preparation method thereof, and belongs to the field of coating. The propeller surface is provided with a wear-resistant and antifouling iron-based amorphous alloy coating formed by thermal spraying of iron-based amorphous alloy powder. The wear-resistant and antifouling iron-based amorphous alloy coating has an antifouling ion release channel. The antifouling ion release channel is formed by the communication of a plating layer metal plated on the surface of the iron-based amorphous alloy powder, and the antifouling ion release channel is in a three-dimensional and stereoscopic communication state. The melting point of the plating layer metal on the surface of the iron-based amorphous alloy powder is lower than the melting point of the iron-based amorphous alloy powder, and the preferred plating layer metal is Cu. The amorphous coating is prepared on the surface of the propeller by using the copper-coated amorphous powder as raw material and ultrasonic flame spraying, and the amorphous coating contains an antifouling ion three-dimensional transmission channel. The amorphous coating has excellent wear resistance and antifouling performance. The method has a simple process, can be practically applied in industry, and has a good application prospect in the field of high-erosion marine antifouling and corrosion prevention.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of propeller preparation, and more particularly relates to a wear-resistant and antifouling propeller and a preparation method thereof. BACKGROUND

[0002] The marine industry has become an important pillar in the economic development of our country, however, the actual marine environment is a very harsh corrosion environment, and the marine equipment serving in the marine environment faces very serious corrosion problems. The annual loss caused by corrosion in our country reaches 5% of GDP, corrosion not only reduces the service life of materials, increases maintenance components, but also seriously endangers life and environmental safety.

[0003] In the marine environment, in addition to the problem of seawater corrosion, there is also the problem of marine biofouling. Marine biofouling generally refers to the colonization of marine organisms (bacteria, algae, hard shell, such as shells, barnacles) attached to underwater structures. Marine biofouling brings many hazards, such as slowing down the speed of ship navigation, increasing energy consumption, and accelerating the corrosion of marine equipment, etc. In order to inhibit the attachment of marine organisms and reduce the damage of marine biofouling to marine equipment, it is extremely crucial to develop an integrated coating for corrosion and fouling prevention.

[0004] At present, the mainstream antifouling coating is a polymer coating, and the polymer coating currently faces many challenges: such as low bonding strength without suitable pretreatment; during long-term exposure, due to mechanical damage and aging effect, it will fail over time; the corrosion resistance of organic antifouling coating has not been paid attention to, and there is a problem of insufficient corrosion resistance.

[0005] In order to solve the above problems of polymer coating, people have developed various metal antifouling coatings containing copper or having special surface properties, but the addition of copper elements will affect the corrosion resistance of the metal antifouling coating, and the underwater antifouling performance of the metal antifouling coating with surface properties is also questioned, and its underwater antifouling performance is not reliable.

[0006] Therefore, it is of great significance to develop a composite coating with wear-resistant, antifouling, corrosion-resistant, low-cost, and high bonding strength functions for the marine field. SUMMARY

[0007] In view of the defects of the prior art, the purpose of the present application is to provide a wear-resistant and antifouling propeller and a preparation method thereof, aiming to solve the problems of insufficient wear-resistant and antifouling comprehensive performance, easy damage and aging, and insufficient bonding strength with the substrate of the existing propeller using organic antifouling coating.

[0008] To achieve the above object, the application provides a wear-resistant and antifouling propeller, which has a wear-resistant and antifouling iron-based amorphous alloy coating formed by thermal spraying of iron-based amorphous alloy powder on the surface of the propeller, and the wear-resistant and antifouling iron-based amorphous alloy coating has antifouling ion release channels formed by the plating layer metal on the surface of the iron-based amorphous alloy powder.

[0009] In the above application concept, the plating layer metal on the surface of the iron-based amorphous alloy powder forms the antifouling ion release channels, which can realize controllable release of antifouling ions, and the construction of the three-dimensional transmission channels of the antifouling ions not only realizes the antifouling function of the coating but also maintains the corrosion resistance of the amorphous coating. The amorphous alloy coating has excellent mechanical durability, and the propeller with the functions of antifouling and corrosion resistance is realized.

[0010] Further, the melting point of the plating layer metal on the surface of the iron-based amorphous alloy powder is lower than that of the iron-based amorphous alloy powder, and preferably, the plating layer metal is Cu, which has the antifouling function.

[0011] Further, the antibacterial adhesion rate of the surface is more than 90%, the anti-algae adhesion rate of the surface is more than 98%, the wear resistance of the wear-resistant and antifouling iron-based amorphous alloy coating is 26 times or more than that of a commercial acrylate coating in a sandpaper wear test, and the self-corrosion current ratio of the wear-resistant and antifouling iron-based amorphous alloy coating is 80 times or more than that of a Q235 substrate.

[0012] In the sandpaper wear test, the sample to be tested is reciprocally rubbed on 2000-mesh sandpaper under a load of 250 g for 200 times, and the stroke is 10 cm each time.

[0013] Further, the thickness of the wear-resistant and antifouling iron-based amorphous alloy coating is 150 μm to 450 μm. The above thickness is suitable for the propeller, because the propeller needs to be as light as possible, and a too thick coating will increase the total mass of the propeller. The coating with a thickness of 150 μm to 450 μm can meet the mass requirement of the propeller.

[0014] Further, the wear-resistant and antifouling iron-based amorphous alloy coating is formed by ultrasonic flame spraying of iron-based amorphous alloy powder with a plating layer of Cu on the surface of the iron-based amorphous alloy powder.

[0015] According to a second aspect of the application, a preparation method of the propeller is also provided, which comprises the following steps:

[0016] S1: sequentially performing cleaning, roughening, sensitization and activation pretreatment on the iron-based amorphous alloy powder, and dissolving metal sulfate, stabilizer, complexing agent and reducing agent to prepare a chemical plating solution,

[0017] S2: mixing the chemical plating solution and the treated amorphous powder obtained in step S1, then cleaning and drying the plating solution and powder to obtain iron-based amorphous powder with a plated Cu layer on the surface,

[0018] S3: surface treatment of the propeller surface to obtain a clean and rough surface,

[0019] S4: deposition of an iron-based amorphous alloy composite coating on the propeller surface by thermal spraying.

[0020] Further, in step S1, the particle size of the iron-based amorphous powder is 30-60 μm. The reason for selecting this particle size range is that the powder in this particle size range has excellent flowability, meeting the requirements of high-velocity oxygen fuel spraying, and the coating obtained by high-velocity oxygen fuel spraying using this particle size powder has the best comprehensive performance.

[0021] The cleaning is specifically: placing the iron-based amorphous powder in anhydrous ethanol, ultrasonic and stirring, then cleaning multiple times with deionized water. The roughening is specifically: placing the cleaned iron-based amorphous powder in a 25-35 wt.% nitric acid solution. The reason for selecting this mass concentration range is that the nitric acid solution at this concentration can roughen the surface of the iron-based amorphous powder without causing significant corrosion of the amorphous powder. Ultrasonic and stirring, then cleaning multiple times with deionized water. The sensitization is specifically: placing the roughened powder in a sensitization solution and stirring, then cleaning with deionized water. The sensitization solution is obtained by adding hydrochloric acid to a stannous chloride dihydrate aqueous solution. The activation is specifically: placing the sensitized powder in an activation solution and stirring to complete the activation. The activation solution is obtained by adding hydrochloric acid to a palladium chloride aqueous solution.

[0022] Further, in step S1, the metal sulfate is copper sulfate pentahydrate, the complexing agent is a mixture of potassium sodium tartrate and disodium ethylenediaminetetraacetate, the stabilizer is a mixture of 2,2-bipyridine and potassium ferrocyanide, and the reducing agent is formaldehyde. The chemical plating solution is adjusted to a pH of 12-13 using NaOH, and the chemical plating is carried out at 40-45°C. The reason for adjusting the pH of the chemical plating solution to 12-13 is that formaldehyde has reducing properties only in an alkaline environment, and Cu 2+ is easy to precipitate in a strong alkaline environment. The reason for carrying out the chemical plating at 40-45°C is that this temperature range can accelerate the rate of chemical plating.

[0023] Further, in step S3, firstly, 60-120 mesh and 300-500 mesh sandpaper are used to polish the surface of the propeller respectively and sequentially, so that a smooth and clean surface is obtained, and then, deionized water and anhydrous ethanol solution are used to ultrasonic clean respectively, and then, drying is performed.

[0024] According to the third aspect of the present application, there is also provided a marine propeller with wear-resistant and antifouling properties.

[0025] In the present application, the amorphous powder is modified by chemical copper plating to introduce copper element, and three-dimensional ion channels are formed in the coating by supersonic flame spraying, the special structure of the three-dimensional ion transmission channels in the amorphous alloy coating enables the amorphous alloy coating to maintain certain corrosion resistance and inherit the mechanical properties of the amorphous coating, and the amorphous alloy coating has excellent mechanical durability.

[0026] In the present application, the amorphous alloy powder with plating layer is sprayed by hot spraying such as supersonic flame spraying to form three-dimensional ion channels in the coating, and the principle is that copper is plated on the surface of the iron-based amorphous powder by chemical plating, and after supersonic flame spraying, a copper-rich region between amorphous regions is formed in the coating in situ, the copper-rich region has a three-dimensional network structure in the coating, in the marine environment, the copper-rich region is eroded by chloride ions to release copper ions, and the copper-rich region with a three-dimensional network structure in the coating becomes a channel for releasing copper ions outward, i.e., a three-dimensional ion channel.

[0027] Overall, compared with the prior art, the above technical solutions conceived by the present application have the following advantages

[0028] Advantages:

[0029] (1) A layer of metal plating layer is chemically plated on the surface of the iron-based amorphous powder, the metal plating layer is connected to form a three-dimensional interconnected channel, and an antifouling ion release channel is formed, this structure can control the metal ion release rate of the amorphous alloy coating, has relatively small environmental pollution, can achieve the antifouling function, and the main part is iron-based amorphous alloy powder, which has good wear resistance, and the iron-based amorphous alloy and the propeller base part are metallurgical combination between metal and metal, and have higher bonding strength.

[0030] (2) The amorphous powder surface is coated with a copper layer, and the copper element exists only at the interface of the amorphous alloy coating, that is, the copper element is released outward through the interface channel, that is, released outward through the anti-fouling ion three-dimensional transmission channel, and has a certain corrosion resistance. Moreover, it inherits the mechanical properties of the iron-based amorphous coating, and has excellent mechanical durability and wear resistance. The iron-based amorphous coating itself is a new type of surface anti-fouling material, and has high wear resistance and high wear resistance. The composite coating of the present application has the characteristics of high substrate universality, strong corrosion resistance, and good wear resistance. Due to the introduction of the plated metal on the surface, it also has the performance of preventing marine organisms from adhering.

[0031] (3) The amorphous alloy coating is prepared by supersonic flame spraying, the plated metal on the surface of the amorphous alloy powder melts under the action of heat in the supersonic flame spraying, and the melted plated metal solidifies to form an anti-fouling ion three-dimensional transmission channel after cooling, and the original excellent performance of the iron-based amorphous alloy is retained. The preparation method of the present application is simple, the process is reliable, the preparation cost is low, and mass production can be carried out. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a structural schematic diagram of the wear-resistant and anti-fouling propeller surface amorphous alloy coating of the embodiment of the present application; it contains an anti-fouling ion three-dimensional transmission channel;

[0033] Figure 2 is a preparation flowchart of the wear-resistant and anti-fouling propeller surface amorphous alloy coating in the embodiment of the present application;

[0034] Figure 3 is a chemical copper plating modification flowchart of the iron-based amorphous powder in the embodiment of the present application;

[0035] Figure 4 is a schematic diagram of preparing the iron-based amorphous alloy coating on the test propeller surface by supersonic flame spraying in the embodiment of the present application;

[0036] Figure 5 (a) in the content is a scanning electron microscope photo of the cross section of the amorphous alloy coating of the embodiment 1 of the present application, Figure 5 (b) in the content is Figure 5 (a) in the content is an EDS photo of the copper element in the scanning electron microscope photo;

[0037] Figure 6 (a) in the content is a scanning electron microscope photo of the longitudinal section of the amorphous alloy coating of the embodiment 1 of the present application, Figure 6 (b) in the content is Figure 6 (a) in the content is an EDS photo of the copper element in the scanning electron microscope photo;

[0038] Figure 7(a) in the content is a transmission electron micrograph of the anti-fouling ion three-dimensional transmission channel of the amorphous alloy coating of the embodiment 1 of the present application, Figure 7 (b) in the content is Figure 7 (a) in the content is an EDS photograph of the copper element of the transmission electron micrograph;

[0039] Figure 8 is an XRD graph of the iron-based amorphous coating obtained by the high-velocity oxygen fuel spraying in the embodiment 1 of the present application;

[0040] Figure 9 is a comparison graph of the anti-pseudomonas aeruginosa adhesion test results of the sample of the embodiment 1 of the present application and the sample of the comparative example;

[0041] Figure 10 is a comparison graph of the anti-staphylococcus aureus adhesion test results of the sample of the embodiment 1 of the present application and the sample of the comparative example;

[0042] Figure 11 is a comparison graph of the anti-chlorella adhesion test results of the sample of the embodiment 1 of the present application and the sample of the comparative example;

[0043] Figure 12 is a comparison graph of the anti-boat algae adhesion test results of the sample of the embodiment 1 of the present application and the sample of the comparative example;

[0044] Figure 13 is a graph of the dynamic polarization curve test results of the embodiment 1 of the present application and the comparative example 1. DETAILED DESCRIPTION

[0045] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0046] The present application provides an amorphous alloy coating containing anti-fouling ion three-dimensional transmission channel, Figure 1 is a structural schematic diagram of an amorphous alloy coating containing anti-fouling ion three-dimensional transmission channel of the embodiment of the present application, as shown in the figure, the amorphous alloy coating has a copper-rich interface region and an amorphous region, the copper-rich interface region is a channel for copper release, and due to the comprehensive effect of the high-velocity oxygen fuel spraying process and the chemical copper plating modification, the anti-fouling ion three-dimensional transmission channel is formed in the coating. The copper-rich interface region releases copper elements to achieve the anti-fouling function, and the amorphous region achieves the wear-resistant and corrosion-resistant function. The composition ratio of the iron-based amorphous coating is, for example, Cu 6.25 Fe 41.9 Co7Cr 14.1 Mo 12.1 C 14.9 B 4.1 Y 1.8(wherein the lower left corner number of each element is the atomic percentage of each element), the material of the propeller in the embodiment is Q235 steel, and the composition is FeMnPSiC. The thickness of the iron-based amorphous alloy coating is 150-450 mu m.

[0047] In combination Figure 1 It can be known that the anti-fouling and wear-resistant mechanism of the amorphous alloy coating is as follows: the copper element is introduced on the surface of the amorphous powder by chemical copper plating modification on the amorphous powder precursor, the copper element is enriched at the interface by preparing the coating through supersonic flame spraying, and the interface serves as a channel for the release of copper outward. The copper ion has broad-spectrum antibacterial performance, can destroy the cell membrane and DNA of bacteria to cause the death of bacteria, and can inhibit the photosynthesis and respiration of algae to achieve the anti-algae effect, so that the amorphous alloy coating has the anti-fouling function. The amorphous region in the amorphous alloy coating can generate a passivation film under the attack of chloride ions, the passivation film can protect the amorphous region from being continuously corroded, and the atomic arrangement of the amorphous region is in a long-range disordered state. Due to the uniform structure of the amorphous state and the generation of the surface passivation film, the iron-based amorphous coating has excellent corrosion resistance in the splashing area with higher salt fog concentration in dry and wet alternating conditions, so that the anti-corrosion function of the amorphous alloy coating is realized. In addition, the amorphous alloy itself has good wear resistance and is not easy to damage and age, and the iron-based amorphous alloy has high bonding strength with the propeller substrate which is also a metal material.

[0048] In engineering practice, a preparation method of the propeller with the amorphous alloy coating containing the anti-fouling ion three-dimensional transmission channel is as shown in Figure 2 , which can include the following steps: Figure 2 , which can include the following steps:

[0049] Step one, the iron-based amorphous powder is subjected to cleaning, roughening, sensitization and activation pretreatment.

[0050] Step two, the metal sulfate, stabilizer, complexing agent and reducing agent are dissolved in deionized water to obtain a chemical plating solution, then the amorphous powder obtained in step one is mixed, and finally cleaning and drying are performed to obtain the surface-coated iron-based amorphous powder.

[0051] Step three, the metal substrate of the propeller is subjected to surface polishing and sand blasting treatment.

[0052] Step four, the iron-based amorphous coating is deposited on the surface of the metal substrate after polishing and sand blasting treatment by thermal spraying.

[0053] Figure 3 is a chemical copper plating modification process schematic diagram of the iron-based amorphous powder in the embodiment of the application, and as shown in the figure, it mainly includes the following steps:

[0054] Step one, 100g iron-based amorphous powder is ultrasonically cleaned in 100ml anhydrous ethanol for 10 minutes, and then cleaned with 100ml deionized water three times,

[0055] Step two, the cleaned iron-based amorphous powder is ultrasonically roughened in a 30wt.% mass fraction nitric acid solution for 20 minutes, and then cleaned with 100ml deionized water three times,

[0056] Step three, the roughened iron-based amorphous powder is sensitized by stirring in a 1L aqueous solution containing 10g stannous chloride dihydrate and 40ml hydrochloric acid for 5 minutes, and then cleaned with 100ml deionized water once,

[0057] Step four, the sensitized iron-based amorphous powder is activated by stirring in a 1L aqueous solution containing 0.25g palladium chloride and 10ml hydrochloric acid for 10 minutes.

[0058] Step five, 25g of metal sulfate copper sulfate pentahydrate, 0.1g of 2-2 bipyridine and potassium ferrocyanide mixed stabilizer, 25g of complexing agent disodium ethylenediaminetetraacetate, 15g of complexing agent potassium sodium tartrate are dissolved in deionized water to obtain a copper plating solution, and then the iron-based amorphous powder obtained in step one is poured into the copper plating solution, the solution PH is adjusted to 12-13 with sodium hydroxide, and finally 40ml of formaldehyde is added, and the surface of the iron-based amorphous powder is coated with copper by plating at 43℃ for 120min.

[0059] Further details are described below in combination with specific examples. Some examples of the present application are completed in the laboratory, the laboratory prepares test propellers of the same material as the actual propeller in the same proportion, and collects seawater and marine organisms for testing. The material of the test propeller in the following examples is Q235 steel.

[0060] Example 1

[0061] (1) Powder pretreatment

[0062] The particle size of the iron-based amorphous powder is 30-40μm. The iron-based amorphous powder is pretreated by cleaning, roughening, sensitizing and activating. 100g of iron-based amorphous powder is ultrasonically cleaned in 100ml of anhydrous ethanol for 10 minutes, and then cleaned with 100ml of deionized water three times. The cleaned iron-based amorphous powder is ultrasonically roughened in a 30wt.% mass fraction nitric acid solution for 20 minutes, and then cleaned with 100ml of deionized water three times. The roughened iron-based amorphous powder is sensitized by stirring in a 1L aqueous solution containing 10g stannous chloride dihydrate and 40ml hydrochloric acid for 5 minutes, and then cleaned with 100ml of deionized water once. The sensitized iron-based amorphous powder is activated by stirring in a 1L aqueous solution containing 0.25g palladium chloride and 10ml hydrochloric acid for 10 minutes.

[0063] (2) Powder electroless copper plating

[0064] 25 g of copper sulfate pentahydrate, 0.1 g of a mixed stabilizer composed of 2-2 bipyridine and potassium ferrocyanide, 25 g of a complexing agent disodium ethylenediaminetetraacetate, and 15 g of a complexing agent potassium sodium tartrate were dissolved in deionized water to obtain a copper plating solution, then the aforementioned obtained iron-based amorphous powder was poured into the copper plating solution, the solution PH was adjusted to 12-13 by sodium hydroxide, and finally 40 ml of formaldehyde was added, and the plating was carried out at 43°C for 120 min, then the iron-based amorphous powder was washed with 200 ml of deionized water for 3 times, and then washed with 100 ml of anhydrous ethanol for 3 times, and the iron-based amorphous powder was vacuum dried at 75°C for 8 h.

[0065] (3) Substrate pretreatment

[0066] The metal substrate surface of the test propeller was polished by using 60-120 mesh and 300-500 mesh sandpaper respectively, the surface of the metal substrate sample was uniformly sandblasted by using a sandblasting machine, a uniform rough surface was formed on the sample surface, then the sample was ultrasonically cleaned with anhydrous ethanol, acetone and deionized water respectively to remove oil and dirt, and finally vacuum dried.

[0067] (4) High velocity oxygen fuel spraying

[0068] Figure 4 is a schematic diagram of the preparation of the iron-based amorphous alloy coating on the surface of the test propeller by using high velocity oxygen fuel spraying in the embodiment of the present application, as shown in the figure, when the iron-based amorphous coating is prepared on the metal substrate by using high velocity oxygen fuel spraying, the spraying moving speed is 450 mm / s, the spraying distance is 300 mm, the step distance is 3 mm, the auxiliary gas is hydrogen, and the powder feeding speed is 25 g / min.

[0069] The cross section of the sprayed iron-based amorphous coating was observed by using a scanning electron microscope, Figure 5 (a) in the content is a scanning electron microscope photograph of the cross section of the amorphous alloy coating of the embodiment 1 of the present application, Figure 5 (b) in the content is Figure 5 (a) in the content is an EDS photograph of the copper element in the scanning electron microscope photograph, Figure 6 (a) in the content is a longitudinal cross section scanning electron microscope photograph of the amorphous alloy coating of the embodiment 1 of the present application, Figure 6 (b) in the content is Figure 6 (a) in the content is an EDS photograph of the copper element in the scanning electron microscope photograph, as shown in the above four figures, the iron-based amorphous coating has obvious layer-by-layer deposition texture interface, and there is enrichment of copper element at the interface.

[0070] Figure 7 (a) in the content is a transmission electron microscope photograph of the anti-fouling ion three-dimensional transmission channel of the amorphous alloy coating of the embodiment 1 of the present application,Figure 7 (b) in the content is Figure 7 The EDS photo of copper element in the transmission electron micrograph shown in (a) in the content, in combination with the two figures, the copper element enrichment exists in the biofilm on the surface of the coating, which shows that the copper element in the iron-based amorphous coating is released into the biofilm. From the transmission electron micrograph, it can be seen that the interface in the coating is a channel for the release of copper ions, and copper is released outward from the release channel.

[0071] Figure 8 The XRD graph of the iron-based amorphous coating obtained by high-velocity oxygen fuel spraying in Example 1 of the present application, from the graph, it can be seen that although copper element is introduced, there is a diffraction peak package at about 45°, which proves that the surface indeed deposits an amorphous coating.

[0072] In this embodiment, the wear-resistant and antifouling iron-based amorphous alloy coating has a thickness of 150 μm to 190 μm. It is found through experiments that the antibacterial adhesion rate on the surface is more than 90%, the anti-algae adhesion rate on the surface is more than 98%, and in the sandpaper abrasion test, the wear resistance of the wear-resistant and antifouling iron-based amorphous alloy coating is 28 times that of the commercial acrylate coating, and the self-corrosion current is 85 times smaller than that of Q235 substrate.

[0073] Example 2

[0074] The difference between this embodiment and Example 1 is that the parameters of each step are different, and the others are similar. The specific differences are:

[0075] (1) Powder pretreatment

[0076] The particle size of the iron-based amorphous powder is 40 μm to 60 μm. The iron-based amorphous powder is pretreated by cleaning, roughening, sensitization and activation. 50 g of iron-based amorphous powder is ultrasonically cleaned in 100 ml of anhydrous ethanol for 10 minutes, and then washed with 100 ml of deionized water three times. The cleaned iron-based amorphous powder is ultrasonically roughened in a 25% mass fraction nitric acid solution for 15 minutes, and then washed with 100 ml of deionized water three times. The roughened iron-based amorphous powder is stirred in a 1L aqueous solution containing 10 g of stannous chloride dihydrate and 40 ml of hydrochloric acid for 5 minutes to complete sensitization, and then washed with 100 ml of deionized water once. The sensitized iron-based amorphous powder is stirred in a 1L aqueous solution containing 0.20 g of palladium chloride and 10 ml of hydrochloric acid for 10 minutes to complete activation.

[0077] (2) Powder chemical copper plating

[0078] Plating is carried out at 40°C for 100 min.

[0079] (4) High-velocity oxygen fuel spraying

[0080] The iron-based amorphous coating is prepared on the metal base of the test propeller by using supersonic flame spraying, the spraying moving speed is 300 mm / s, the spraying distance is 320 mm, the step distance is 3 mm, the auxiliary gas is hydrogen, and the powder feeding speed is 30 g / min.

[0081] The cross section of the sprayed iron-based amorphous coating is observed by using a scanning electron microscope. In this embodiment, the thickness of the wear-resistant and antifouling iron-based amorphous alloy coating is 180 μm to 230 μm. It is found through tests that the antibacterial adhesion rate of the surface is more than 90%, the antialgal adhesion rate of the surface is more than 98%, in the sandpaper abrasion test, the wear resistance of the wear-resistant and antifouling iron-based amorphous alloy coating is 32 times that of the commercial acrylate coating, and the self-corrosion current is 90 times smaller than that of the Q235 base.

[0082] Embodiment 3

[0083] This embodiment is different from embodiment 1 in that the parameters of each step are different, and the others are similar. The specific differences are as follows:

[0084] (1) Powder pretreatment

[0085] The particle size of the iron-based amorphous powder is 45 μm to 55 μm. The iron-based amorphous powder is pretreated by cleaning, roughening, sensitization and activation. 25 g of the iron-based amorphous powder is ultrasonically cleaned in 100 ml of anhydrous ethanol for 10 minutes, and then cleaned with 100 ml of deionized water three times. The cleaned iron-based amorphous powder is ultrasonically roughened in a 35% mass fraction nitric acid solution for 12 minutes, and then cleaned with 100 ml of deionized water three times. The roughened iron-based amorphous powder is stirred in a 1 l aqueous solution containing 10 g of stannous chloride dihydrate and 40 ml of hydrochloric acid for 5 minutes to complete sensitization, and then cleaned with 100 ml of deionized water once. The sensitized iron-based amorphous powder is stirred in a 1 l aqueous solution containing 0.15 g of palladium chloride and 10 ml of hydrochloric acid for 10 minutes to complete activation.

[0086] (2) Powder chemical copper plating

[0087] The plating is performed at 45°C for 90 min.

[0088] (4) Supersonic flame spraying

[0089] The iron-based amorphous coating is prepared on the metal base by using supersonic flame spraying, the spraying moving speed is 600 mm / s, the spraying distance is 350 mm, the step distance is 3 mm, the auxiliary gas is hydrogen, and the powder feeding speed is 20 g / min.

[0090] The cross section of the sprayed iron-based amorphous coating is observed by scanning electron microscopy. In this embodiment, the wear-resistant and anti-fouling iron-based amorphous alloy coating has a thickness of 390 μm to 450 μm. It is found through experiments that the antibacterial adhesion rate of the surface is more than 90%, the anti-algae adhesion rate of the surface is more than 98%, in the sandpaper abrasion test, the wear resistance of the wear-resistant and anti-fouling iron-based amorphous alloy coating is 29 times that of the commercial acrylate coating, and the self-corrosion current is 86 times smaller than that of the Q235 substrate.

[0091] Embodiment 4

[0092] S1: The particle size of the iron-based amorphous powder is 30 μm to 40 μm. The iron-based amorphous alloy powder is sequentially subjected to cleaning, roughening, sensitization, and activation pretreatment. A chemical plating solution is prepared by dissolving a metal sulfate, a stabilizer, a complexing agent, and a reducing agent.

[0093] The cleaning is specifically placing the iron-based amorphous powder in anhydrous ethanol, ultrasonic and stirring, and then cleaning multiple times with deionized water. The roughening is specifically placing the cleaned iron-based amorphous powder in a 25 wt.% nitric acid solution, ultrasonic and stirring, and then cleaning multiple times with deionized water. The sensitization is specifically placing the roughened powder in a sensitization solution, stirring, and then cleaning with deionized water, wherein the sensitization solution is obtained by adding hydrochloric acid to a stannous chloride dihydrate aqueous solution. The activation is specifically placing the sensitized powder in an activation solution, stirring, and then completing, wherein the activation solution is obtained by adding hydrochloric acid to a palladium chloride aqueous solution.

[0094] The metal sulfate is copper sulfate pentahydrate, the complexing agent is a mixture of potassium sodium tartrate and disodium ethylenediaminetetraacetate, the stabilizer is a mixture of 2,2-bipyridine and potassium ferrocyanide, and the reducing agent is formaldehyde. The chemical plating solution is adjusted to a pH of 12 using NaOH, and the chemical plating is carried out at 40°C.

[0095] S2: The chemical plating solution obtained in step S1 and the treated amorphous powder are mixed, and then the plating solution powder is cleaned and dried to obtain an iron-based amorphous powder with a Cu plating layer on the surface,

[0096] S3: The surface of the propeller is treated to obtain a clean and rough surface. In step S3, first, 60-120 mesh and 300-500 mesh sandpaper are used to polish the surface of the iron-based amorphous coating, respectively, to obtain a smooth and clean surface. Then, deionized water and anhydrous ethanol solution are used for ultrasonic cleaning, respectively, and then dried.

[0097] S4: An iron-based amorphous alloy composite coating is deposited on the surface of the propeller by thermal spraying. In step S4, the thermal spraying method is supersonic flame spraying, the spraying moving speed is 300 mm / s, the spraying distance is 300 mm, the auxiliary gas is hydrogen, and the powder feeding speed is 30 g / min.

[0098] The cross section of the sprayed iron-based amorphous coating is observed by scanning electron microscopy. In this embodiment, the wear-resistant and anti-fouling iron-based amorphous alloy coating has a thickness of 300-400 μm. It is found through tests that the antibacterial adhesion rate of the surface is more than 90%, the anti-algae adhesion rate of the surface is more than 98%, the wear resistance of the wear-resistant and anti-fouling iron-based amorphous alloy coating is 28 times that of a commercial acrylate coating in a sandpaper abrasion test, and the self-corrosion current of the coating is 81 times smaller than that of a Q235 substrate.

[0099] Embodiment 5

[0100] S1: The particle size of the iron-based amorphous powder is 50-60 μm. The iron-based amorphous alloy powder is sequentially subjected to cleaning, roughening, sensitization and activation pretreatment. A chemical plating solution is prepared by dissolving a metal sulfate, a stabilizer, a complexing agent and a reducing agent,

[0101] The cleaning is specifically as follows: the iron-based amorphous powder is placed in anhydrous ethanol, ultrasonically treated and stirred, and then cleaned with deionized water multiple times. The roughening is specifically as follows: the cleaned iron-based amorphous powder is placed in a 35 wt.% nitric acid solution, ultrasonically treated and stirred, and then cleaned with deionized water multiple times. The sensitization is specifically as follows: the roughened powder is placed in a sensitization solution and stirred, and then cleaned with deionized water. The sensitization solution is obtained by adding hydrochloric acid to a water solution of stannous chloride dihydrate. The activation is specifically as follows: the sensitized powder is placed in an activation solution and stirred to complete the activation. The activation solution is obtained by adding hydrochloric acid to a water solution of palladium chloride.

[0102] In step S1, the metal sulfate is copper sulfate pentahydrate, the complexing agent is a mixture of potassium sodium tartrate and disodium ethylenediaminetetraacetate, the stabilizer is a mixture of 2,2-bipyridine and potassium ferrocyanide, and the reducing agent is formaldehyde. The chemical plating solution is adjusted to a pH of 13 with NaOH, and the chemical plating is performed at 45°C.

[0103] S2: The chemical plating solution obtained in step S1 and the treated amorphous powder are mixed, and then the plating solution and the powder are cleaned and dried to obtain iron-based amorphous powder with a Cu plating layer on the surface,

[0104] S3: The surface of the propeller is subjected to surface treatment to obtain a clean and rough surface,

[0105] In step S3, first, the iron-based amorphous coating surface is polished with 60-120 mesh and 300-500 mesh sandpaper, respectively, to obtain a smooth and clean surface. Then, the surface is ultrasonically cleaned with deionized water and anhydrous ethanol solution, respectively, and then dried.

[0106] S4: depositing the iron-based amorphous alloy composite coating on the surface of the propeller by thermal spraying. In step S4, the thermal spraying method is high-velocity oxygen fuel spraying, the spraying moving speed is 600 mm / s, the spraying distance is 350 mm, the auxiliary gas is hydrogen, and the powder feeding speed is 30 g / min.

[0107] The cross section of the sprayed iron-based amorphous coating is observed by a scanning electron microscope. In this embodiment, the wear-resistant and antifouling iron-based amorphous alloy coating has a thickness of 150 μm to 270 μm. It is found through tests that the antibacterial adhesion rate of the surface is more than 90%, the antialgal adhesion rate of the surface is more than 98%, the wear resistance of the wear-resistant and antifouling iron-based amorphous alloy coating is 28 times that of a commercial acrylate coating in a sandpaper abrasion test, and the self-corrosion current is 81 times smaller than that of the Q235 substrate.

[0108] Comparative examples

[0109] The present application has two comparative examples, as shown in Table 1 below. In the two comparative examples, the Q235 substrate without spraying and the amorphous coating without chemical copper plating modification are given.

[0110] Table 1: Coating information of specific examples and comparative examples

[0111] Numbering Amorphous coating Comparative Example 1 None Comparative Example 2 Amorphous coating without three-dimensional transport channels for antifouling ions Example 1 Amorphous coating with three-dimensional transport channels for antifouling ions

[0112] Figure 9 is a comparison chart of the anti-pseudomonas aeruginosa adhesion test results of the sample of Example 1 of the present application and the sample of the comparative example, Figure 10 is a comparison chart of the anti-staphylococcus aureus adhesion test results of the sample of Example 1 of the present application and the sample of the comparative example, and Figure 9 It can be seen that the pseudomonas aeruginosa adhered to the surface of the amorphous coating containing the antifouling ion three-dimensional transmission channel (Example 1) is much less than that adhered to the surface of the Q235 substrate (Comparative Example 1) and the amorphous coating not containing the antifouling ion three-dimensional transmission channel (Comparative Example 2). From Figure 10 It can be seen that the staphylococcus aureus adhered to the surface of the amorphous coating containing the antifouling ion three-dimensional transmission channel (Example 1) is much less than that adhered to the surface of the Q235 substrate (Comparative Example 1) and the amorphous coating not containing the antifouling ion three-dimensional transmission channel (Comparative Example 2), indicating that the amorphous coating containing the antifouling ion three-dimensional transmission channel can effectively resist the adhesion of bacteria on the surface of the amorphous alloy coating, and has excellent antibacterial adhesion performance, meeting the requirements of the antifouling performance.

[0113] Figure 11 is a comparison chart of the anti-chlorella adhesion test results of the sample of Example 1 of the present application and the sample of the comparative example, Figure 12is a comparison chart of anti-Navicula algae adhesion test results of the sample of example 1 and the sample of the comparative example, the sample of example 1 and the sample of the comparative example are immersed in algae liquid of chlorella and Navicula algae in a constant temperature and humidity incubator for 7 days, and the adhesion area of diatoms on the surface of the sample is observed and counted by using a fluorescence microscope, and the anti-algae adhesion rate is calculated. Figure 11 It can be seen that, after 7 days, the anti-chlorella adhesion rate of the amorphous alloy coating containing the anti-fouling ion three-dimensional transmission channel (example 1) reaches 98.87%, while the anti-chlorella adhesion rate of the amorphous alloy coating not containing the anti-fouling ion three-dimensional transmission channel (comparative example 2) is 94.59%, and the anti-chlorella adhesion rate of the Q235 substrate without spraying the coating (comparative example 1) is 63.59%. It can be seen from Figure 12 that the anti-Navicula algae adhesion rate of the amorphous alloy coating containing the anti-fouling ion three-dimensional transmission channel (example 1) reaches 99.26%, while the anti-Navicula algae adhesion rate of the amorphous alloy coating not containing the anti-fouling ion three-dimensional transmission channel (comparative example 2) is 97.57%, and the anti-Navicula algae adhesion rate of the Q235 substrate without spraying the coating (comparative example 1) is only 49.72%, which shows that the amorphous alloy coating containing the anti-fouling ion three-dimensional transmission channel has excellent anti-algae adhesion performance.

[0114] The corrosion resistance of example 1 and comparative example 1 is compared by using dynamic polarization curve test, and the results are shown in Figure 13 Figure 13 is a dynamic polarization curve test result chart of example 1 and comparative example 1, as can be seen from the chart, the corrosion current and the corrosion potential reflect the corrosion resistance of the sample, the lower the corrosion current, the greater the corrosion potential, and the better the corrosion resistance. It can be seen from Figure 13 that the corrosion potential of example 1 is-544.7mV, and the corrosion current is 86.65nA / cm 2 , the corrosion potential of comparative example 1 is-724mV, and the corrosion current is 6965.76nA / cm 2 , it can be seen that the corrosion current of example 1 is smaller than that of comparative example 1, and the corrosion potential of example 1 is greater than that of comparative example 1. It shows that the addition of the iron-based amorphous alloy coating improves the corrosion resistance of the sample.

[0115] In the present application, the iron-based amorphous powder is modified by chemical copper plating, and the amorphous composite coating containing the anti-fouling ion three-dimensional transmission channel is prepared by supersonic flame spraying, the coating has excellent mechanical durability, has the advantages of integration of anti-corrosion and anti-fouling functions, and has excellent anti-marine biofouling ability and corrosion resistance.

[0116] In the present application, the iron-based amorphous powder can also be Fe 48 Mo 14 Cr 15 Y2C​15 B6, Fe 49.7 Cr 18 Mn 1.9 Mo 7.4 W 1.6 B 15. 2C 3.8 Si 2.4 and so on.

[0117] It is to be understood that the above description is far from being exhaustive, and that many modifications and further meanings can be suggested to one skilled in the art, and yet fall within the scope of the present application as outlined by the following claims.

Claims

1. A wear-resistant and anti-fouling propeller, characterized in that, Its surface has a wear-resistant and anti-fouling iron-based amorphous alloy coating formed by thermal spraying of iron-based amorphous alloy powder. The wear-resistant and anti-fouling iron-based amorphous alloy coating has anti-fouling ion release channels, which are formed by interconnected coating metals on the surface of the iron-based amorphous alloy powder. The anti-fouling ion release channels are three-dimensional and interconnected. The melting point of the coating metal on the surface of the iron-based amorphous alloy powder is lower than that of the iron-based amorphous alloy powder itself, and the coating metal is Cu. Specifically, copper is electrolessly plated onto the surface of iron-based amorphous alloy powder. After being sprayed with a supersonic flame, the coating metal on the surface of the amorphous alloy powder melts under the thermal action of the supersonic flame. The molten coating metal solidifies after cooling to form a three-dimensional anti-fouling ion transport channel.

2. The wear-resistant and anti-fouling propeller as described in claim 1, characterized in that, The wear-resistant and anti-fouling iron-based amorphous alloy coating has a thickness of 150 μm to 450 μm.

3. A method for preparing a wear-resistant and anti-fouling propeller as described in any one of claims 1-2, characterized in that, It is made by spraying iron-based amorphous alloy powder with a Cu coating on the surface of the propeller using a supersonic flame spraying method.

4. The method as described in claim 3, characterized in that, It includes the following steps: S1: The iron-based amorphous alloy powder is subjected to a series of pretreatments including cleaning, roughening, sensitization, and activation. A chemical plating solution is prepared by dissolving metal sulfates, stabilizers, complexing agents, and reducing agents. S2: The chemical plating solution obtained in step S1 is mixed with the treated amorphous powder, and then the plating solution powder is cleaned and dried to obtain an iron-based amorphous alloy powder with a Cu coating on the surface. S3: Perform surface treatment on the propeller surface to obtain a clean yet rough surface. S4: Deposit an iron-based amorphous alloy composite coating on the propeller surface using a supersonic flame spraying method.

5. The method as described in claim 4, characterized in that, In step S1, the iron-based amorphous alloy powder has a particle size of 30 μm to 60 μm. The cleaning process involves placing the iron-based amorphous alloy powder in anhydrous ethanol, ultrasonicating and stirring, followed by multiple washes with deionized water. The roughening process specifically involves placing the cleaned iron-based amorphous alloy powder in a 25wt.%–35wt.% nitric acid solution, ultrasonicating and stirring, followed by multiple rinses with deionized water. The sensitization process involves placing the coarsened powder in a sensitizing solution and stirring, followed by washing with deionized water. The sensitizing solution is obtained by adding hydrochloric acid to an aqueous solution of stannous chloride dihydrate. The activation process involves placing the sensitized powder in an activation solution and stirring. The activation solution is obtained by adding hydrochloric acid to an aqueous solution of palladium chloride.

6. The method as described in claim 5, characterized in that, In step S1, the metal sulfate is copper sulfate pentahydrate, the complexing agent is a mixture of potassium sodium tartrate and disodium ethylenediaminetetraacetate, the stabilizer is a mixture of 2,2-bipyridine and potassium ferrocyanide, and the reducing agent is formaldehyde. The pH of the chemical plating solution was adjusted to 12-13 using NaOH, and chemical plating was carried out at 40℃-45℃.

7. The method as described in claim 6, characterized in that, In step S3, firstly, the propeller surface was polished with 60-120 grit and 300-500 grit sandpaper respectively to obtain a smooth and clean surface. Then, it was ultrasonically cleaned with deionized water and anhydrous ethanol solution respectively, and then dried. In step S4, during supersonic flame spraying, the spraying moving speed is 300~600 mm / s, the spraying distance is 300~350 mm, hydrogen is used as the auxiliary gas, and the powder feeding speed is 20~30 g / min.

8. A marine vessel, characterized in that, It includes a wear-resistant and anti-fouling propeller as described in any one of claims 1-2.

Images