Ketjen black loaded high-entropy alloy anticorrosive coating as well as preparation method and application thereof

Abstract

The invention provides a Ketjen black loaded high-entropy alloy anticorrosive coating as well as a preparation method and application thereof, and relates to the technical field of surface modification coatings. The preparation method of the Ketjen black loaded high-entropy alloy anti-corrosion coating comprises the following steps that the surface of a base material is pretreated and then coated with a layer of carbon glue, and a carbon glue transition layer is obtained; ketjen black powder and methyl alcohol are mixed and then coated on the surface of the carbon glue transition layer, and a Ketjen black layer is obtained after drying; and depositing a CoCrFeMnNi high-entropy alloy coating on the surface of the ketjen black layer by adopting a magnetron sputtering method to obtain the ketjen black loaded high-entropy alloy anticorrosive coating. The Ketjen black loaded high-entropy alloy anti-corrosion coating is prepared on the flexible sensor substrate through the technology of combining coating and magnetron sputtering, the conductivity of the composite coating is improved through a three-dimensional conductive network of Ketjen black, meanwhile, the Ketjen black inhibits propagation of microcracks and promotes interface friction energy dissipation, and the corrosion resistance of the composite coating is improved. And the wear resistance of the composite coating is obviously enhanced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of surface modification coating, in particular to a Ketjen black loaded high-entropy alloy corrosion resistant coating and a preparation method and application thereof. BACKGROUND

[0002] In recent years, wearable flexible sensors have attracted much attention due to their wide applications in health monitoring, motion tracking and human-computer interaction. The core function of such devices relies on the stable electrical performance of electrodes, signal transmission lines and contact interfaces under dynamic deformation environment. However, flexible sensors face multiple challenges in practical applications: on the one hand, repeated bending, stretching and friction caused by human activities can lead to fatigue fracture or interface peeling of traditional metal coatings (such as silver, copper); on the other hand, sweat, moisture and corrosive media in the external environment are easy to cause metal oxidation or electrochemical corrosion, resulting in a decrease in conductivity and even functional failure. In addition, mechanical wear during long-term wear can further accelerate the degradation of coating performance. Therefore, the development of flexible interface materials with high conductivity, corrosion resistance and wear resistance has become a key technical bottleneck in this field.

[0003] Traditional solutions mostly use noble metal (gold, platinum, etc.) nano-coating or conductive polymer composite, but their high cost or insufficient mechanical properties limit large-scale applications. High-entropy alloys have excellent hardness, strength, wear resistance and corrosion resistance due to their high-entropy effect in thermodynamics, sluggish diffusion effect in kinetics, lattice distortion effect in structure and "cocktail" effect in performance. However, the conductivity of single high-entropy alloy coating is limited by the electron scattering effect of solid solution structure, and the nanoscale coating on the flexible substrate is easy to cause micro-crack propagation due to stress concentration, resulting in cross-section failure under long-term cyclic load. To overcome the above limitations, the composite modification of carbon-based nanomaterials and metal coatings has become a new research idea. Among them, Ketjen black (KB) can be used as an ideal electron transport enhancer due to its unique ultra-high three-dimensional conductive network density and mesoporous structure. By loading Ketjen black nanoparticles in the high-entropy alloy coating matrix, on the one hand, a fast conductive path can be constructed to compensate for the insufficient intrinsic conductivity of the high-entropy alloy coating; on the other hand, the graphene-like sheet structure of Ketjen black can effectively inhibit the propagation of micro-cracks, and through the interface friction energy dissipation mechanism, the wear resistance of the coating can be improved. In addition, the chemical inertness of Ketjen black can cooperate with the passivation effect of the high-entropy alloy coating to form a dense composite oxide film on the surface of the coating, significantly improving the corrosion resistance of the system.

[0004] Current research and invention focus on composite coatings on rigid substrates, while there is still a gap in the adaptability research and invention of flexible sensors such as fibers / textiles. The technical difficulties lie in the need for atomic-level bonding between the low thickness of the nano-coating and the fiber surface to resist dynamic deformation; the synergistic corrosion mechanism of the multi-scale interface (fiber-coating-medium) needs to be inhibited by gradient design; the intrinsic flexibility of the coating is in conflict with the strong metal bond characteristics of the high-entropy alloy coating.

[0005] To improve the sweat corrosion resistance of electronic coatings, invention 202311768957.6 discloses an electronic protective coating synthesized by using rubber-type macromolecular polymer, terpene resin, environmentally friendly solvent, silane coupling agent, defoaming agent, fluorescent indicator and antioxidant. The protective coating prepared by the invention has low viscosity, easy spraying, good flow and defoaming effect, good flexibility, can effectively protect electronic components with R angle and other protruding parts, effectively resist long-term powered sweat test, and has high bonding reliability. However, the coating of the invention has the problems of insufficient bonding strength with the substrate, and poor wear resistance, corrosion resistance and conductivity. SUMMARY

[0006] The purpose of the present application is to provide a ketchen black loaded high-entropy alloy corrosion resistant coating and its preparation method and application, to solve the problems of insufficient bonding strength with the substrate, poor wear resistance, weak corrosion resistance and poor conductivity of the existing corrosion resistant coating for flexible sensors.

[0007] In order to achieve the above-mentioned purpose of the invention, the present application provides the following technical solutions:

[0008] The present application provides a preparation method of a ketchen black loaded high-entropy alloy corrosion resistant coating, comprising the following steps:

[0009] 1) After pretreating the surface of the substrate material, a layer of carbon glue is coated to obtain a carbon glue transition layer;

[0010] 2) Mix the ketchen black powder with methanol and coat it on the surface of the carbon glue transition layer, and dry to obtain a ketchen black layer;

[0011] 3) Use magnetron sputtering method to deposit CoCrFeMnNi high-entropy alloy coating on the surface of the ketchen black layer to obtain a ketchen black loaded high-entropy alloy corrosion resistant coating.

[0012] Preferably, the substrate material in step 1) can be selected from one of a polymer film, a paper-based material, a metal foil, and a graphene material;

[0013] The pretreatment includes sanding, polishing and ultrasonic cleaning;

[0014] The roughness of the substrate surface after pretreatment is 1-2 nm.

[0015] Preferably, the carbon glue in step 1) is made of carbon-containing base polymer and nano-carbon filler;

[0016] The thickness of the glue carbon transition layer is 0.1-0.5mm.

[0017] Preferably, the apparent bulk density of the Ketjen black powder in step 2) is 125-145kg / m 3 ;

[0018] The particle size of the Ketjen black powder is 44-50μm;

[0019] The oil absorption value of the Ketjen black powder is 310-345mL / 100g;

[0020] The sand content of the Ketjen black powder is ≤30mg / kg;

[0021] The moisture of the Ketjen black powder is ≤0.5%;

[0022] The volatile matter of the Ketjen black powder is ≤1%;

[0023] The iodine absorption value of the Ketjen black powder is 780-840mg / g;

[0024] The ash content of the Ketjen black powder is ≤0.05%;

[0025] The specific surface area of the Ketjen black powder is 780-840m 2 / g;

[0026] The specific resistance of the Ketjen black powder is 0.5-2Ω·cm;

[0027] The pH value of the Ketjen black powder is 8-10;

[0028] The coating amount of the Ketjen black powder is 20-50mg / cm 2 .

[0029] Preferably, the parameters of the magnetron sputtering method in step 3) are as follows:

[0030] The system is a non-equilibrium magnetron sputtering deposition system;

[0031] The vacuum degree is ≤5×10 -4 Pa;

[0032] The argon gas is continuously introduced during the magnetron sputtering process, and the flow rate of the argon gas is 20-30sccm;

[0033] The opening degree of the gate valve for controlling the working pressure in the magnetron sputtering is 10-20%;

[0034] The working pressure of the resistance gauge is 0.3-0.5Pa;

[0035] The working pressure of the film gauge is 1.0-2.0 Pa;

[0036] The magnetron sputtering power is 100-120 W;

[0037] The substrate bias is -100--80 V;

[0038] The deposition time is 100-140 min.

[0039] Preferably, the CoCrFeMnNi high-entropy alloy coating in step 3) is in an equimolar atomic ratio.

[0040] The application provides a Korich black loaded high-entropy alloy corrosion-resistant coating prepared by the preparation method.

[0041] The application further provides application of the Korich black loaded high-entropy alloy corrosion-resistant coating in a sensor.

[0042] The application has at least the following beneficial effects:

[0043] The application uses a combination of coating and magnetron sputtering to prepare a Korich black nanoparticle enhanced corrosion-resistant CoCrFeMnNi high-entropy alloy composite coating on different substrate materials. The three-dimensional conductive network of Korich black not only improves the conductivity of the composite coating, but also significantly enhances the wear resistance of the composite coating by inhibiting the expansion of micro-cracks and promoting the dissipation of interface friction energy. In the application, the magnetron sputtering technology is used to realize atomic-level bonding between the high-entropy alloy coating and the flexible substrate, effectively avoiding the peeling failure problem commonly seen at the heterogeneous interface. The strong interface bonding and the inherent excellent corrosion resistance of the high-entropy alloy not only endow the composite coating with excellent comprehensive corrosion resistance, but also ensure good bonding force between the composite coating and the flexible substrate. The synergistic improvement of the above-mentioned conductivity, wear resistance, interface bonding force and corrosion resistance significantly enhances the long-term reliability and stability of the composite coating in the actual complex service environment (mechanical stress, chemical corrosion medium and other multi-factor coupling) of the flexible sensor. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 FIG. 1 is an SEM image of the Korich black loaded high-entropy alloy corrosion-resistant coating prepared in Example 1 of the application;

[0045] Figure 2 FIG. 2 is an XPS spectrum of the junction between the Korich black layer and the high-entropy alloy layer in the Korich black loaded high-entropy alloy corrosion-resistant coating prepared in Example 2 of the application, Figure 2 wherein a-f are photoelectron spectra of C element, Co element, Cr element, Fe element, Mn element and Ni element, respectively;

[0046] Figure 3The Raman spectrum of the ketchen black loaded high-entropy alloy corrosion resistant coating prepared in Example 2 of the present application;

[0047] Figure 4 The potentiodynamic polarization curves of the ketchen black loaded high-entropy alloy corrosion resistant coating prepared in Example 3, Comparative Example 1 and Comparative Example 2 of the present application and the 304ss substrate without corrosion treatment in a 3.5wt.% sodium chloride solution. DETAILED DESCRIPTION

[0048] The present application provides a preparation method of a ketchen black loaded high-entropy alloy corrosion resistant coating, comprising the following steps:

[0049] 1) coating a layer of carbon glue on the surface of the substrate material after pretreatment to obtain a carbon glue transition layer;

[0050] 2) coating the ketchen black powder mixed with methanol on the surface of the carbon glue transition layer, and drying to obtain a ketchen black layer;

[0051] 3) depositing a CoCrFeMnNi high-entropy alloy coating on the surface of the ketchen black layer by magnetron sputtering to obtain a ketchen black loaded high-entropy alloy corrosion resistant coating.

[0052] In the present application, the substrate material in step 1) can be selected from one of a polymer film, a paper-based material, a metal foil and a graphene material.

[0053] The polymer film can be selected from a polyimide film, a polyethylene terephthalate film, a polydimethylsiloxane film or a polyurethane film; the paper-based material can be selected from cellulose paper; the metal foil can be selected from a stainless steel foil, a titanium foil or an aluminum foil; and the graphene material can be selected from a graphene film or an oxidized graphene film.

[0054] In the present application, the pretreatment includes grinding, polishing and ultrasonic cleaning, and the specific treatment method is as follows: grinding the substrate with sandpaper of different particle sizes, polishing to mirror effect, and then ultrasonic cleaning in acetone, anhydrous ethanol and deionized water for 10-20 min to remove grease and impurities on the surface of the substrate; the roughness of the surface of the substrate after pretreatment is 1-2 nm, preferably 1.2-1.8 nm, further preferably 1.4-1.6 nm, and more preferably 1.5 nm.

[0055] In the present application, the carbon glue in step 1) is made of carbon-containing base polymer and nano-carbon filler; the carbon-containing base polymer includes one or more of polythiophene, polyaniline and polypyrrole, and the nano-carbon filler includes one or more of carbon nanotube, graphene oxide and graphene nanosheet.

[0056] In the present application, the thickness of the glue carbon transition layer is 0.1-0.5 mm, preferably 0.2-0.4 mm, further preferably 0.25-0.35 mm, and more preferably 0.3 mm.

[0057] In the present application, the carbon glue transition layer is a functional interface transition layer, which plays the role of conductive bonding, mechanical support, interface compatibility, surface morphology adaptation, and electrochemical test compatibility.

[0058] The carbon glue has high adhesion and rheological properties, which can uniformly disperse the ketchen black powder on the surface of the stainless steel substrate to form a continuous and dense carbon material layer, avoid powder shedding or aggregation, realize interface anchoring and spatial limited dispersion of the ketchen black powder, and reduce the interface stress and promote the chemical bonding between the coatings.

[0059] Preferably, the apparent bulk density of the ketchen black powder in step 2) is 125-145 kg / m 3 , preferably 128-142 kg / m 3 , further preferably 130-140 kg / m 3 , and more preferably 132-138 kg / m 3 .

[0060] In the present application, the particle size of the ketchen black powder is 44-50 μm, preferably 45-49 μm, further preferably 46-48 μm, and more preferably 47 μm;

[0061] The oil absorption value of the ketchen black powder is 310-345 mL / 100 g, preferably 315-340 mL / 100 g, further preferably 320-335 mL / 100 g, and more preferably 325-330 mL / 100 g;

[0062] The sand content of the ketchen black powder is ≤30 mg / kg, preferably 5-30 mg / kg, further preferably 10-25 mg / kg, and more preferably 15-20 mg / kg;

[0063] The moisture content of the ketchen black powder is ≤0.5%, preferably 0.01-0.55, further preferably 0.05-0.4%, and more preferably 0.1-0.3%;

[0064] The volatile matter content of the ketchen black powder is ≤1%, preferably 0.01-1%, further preferably 0.05-0.5%, and more preferably 0.1-0.3%;

[0065] The iodine absorption value of the Ketjen black powder is 780-840 mg / g, preferably 790-830 mg / g, more preferably 800-820 mg / g, and even more preferably 810 mg / g;

[0066] The ash content of the Ketjen black powder is ≤0.05%, preferably 0.01-0.05%, more preferably 0.02-0.03%, and even more preferably 0.03%.

[0067] The specific surface area of ​​the Ketjen black powder is 780–840 m². 2 / g, preferably 790-830m 2 / g, further preferably 800-820m 2 / g, more preferably 810m 2 / g;

[0068] The resistivity of the Ketjen black powder is 0.5 to 2 Ω·cm, preferably 0.7 to 1.8 Ω·cm, more preferably 1 to 1.5 Ω·cm, and even more preferably 1.2 Ω·cm;

[0069] The pH value of the Ketjen black powder is 8-10, preferably 8.5-9.5, and more preferably 9;

[0070] The coating amount of Ketjen black powder is 20-50 mg / cm². 2 The preferred concentration is 25–45 mg / cm³. 2 More preferably 30–40 mg / cm³ 2 More preferably 35 mg / cm 2 .

[0071] In this invention, the coating method of the Ketjen black powder is to disperse the Ketjen black powder in methanol and then coat it on the surface of the carbon adhesive transition layer, and then vacuum dry it to obtain the Ketjen black layer.

[0072] The Ketjen black powder has a mass concentration of 5% in methanol, and is vacuum dried at a temperature of 100°C for 1 hour.

[0073] In this invention, the parameters of the magnetron sputtering method described in step 3) are as follows:

[0074] The system is a non-equilibrium magnetron sputtering deposition system;

[0075] Vacuum degree ≤5×10 -4 Pa, preferably 5 × 10 -5 ~4×10 -4 Pa, more preferably 1×10 -4 ~3×10 - 4 Pa, more preferably 2×10 Pa -4Pa;

[0076] The argon gas is continuously introduced in the process of magnetron sputtering, the flow rate of the argon gas is 20-30 sccm, preferably 22-28 sccm, further preferably 24-26 sccm, and more preferably 25 sccm;

[0077] The opening degree of the gate valve for controlling the working pressure in the magnetron sputtering is 10-20%, preferably 12-18%, further preferably 14-16%, and more preferably 15%;

[0078] The working pressure of the resistance gauge is 0.3-0.5 Pa, preferably 0.35-0.45 Pa, further preferably 0.38-0.42 Pa, and more preferably 0.4 Pa;

[0079] The working pressure of the thin film gauge is 1.0-2.0 Pa, preferably 1.2-1.8 Pa, further preferably 1.4-1.6 Pa, and more preferably 1.5 Pa;

[0080] The magnetron sputtering power is 100-120 W, preferably 103-118 W, further preferably 105-115 W, and more preferably 108-112 W;

[0081] The substrate bias is -100 to -80 V, preferably -98 to -83 V, further preferably -95 to -85 V, and more preferably -92 to -88 V;

[0082] The deposition time is 100-140 min, preferably 105-135 min, further preferably 110-130 min, and more preferably 115-125 min.

[0083] In the present application, the CoCrFeMnNi high-entropy alloy coating in step 3) is in an equimolar atomic ratio.

[0084] The present application provides a Korich black loaded high-entropy alloy corrosion resistant coating prepared by the above preparation method.

[0085] The present application also provides an application of the above Korich black loaded high-entropy alloy corrosion resistant coating in a sensor.

[0086] The technical solutions provided by the present application will be described in detail below in combination with embodiments, but they should not be understood as limiting the scope of protection of the present application.

[0087] Example 1

[0088] (1) Surface treatment of the substrate: polish the 304ss substrate with sandpaper of different grits and polish to mirror effect, with a surface roughness of 1.5 nm. Ultrasonically clean the polished 304ss substrate in acetone, anhydrous ethanol and deionized water for 15 minutes, respectively, to remove grease and impurities on the surface of the substrate.

[0089] (2) Adhere a carbon adhesive transition layer with a thickness of 0.2 mm on the surface of the 304ss substrate (carbon adhesive: Kailiao brand KH11252 double-sided carbon conductive adhesive tape, 20 mm*25 m (non-woven fabric)).

[0090] (3) Disperse Ketjen black powder (Ketjenblack EC-300J, apparent bulk density 130 kg / m 3 , particle size 48 μm) in methanol at a concentration of 5 wt.% to obtain a dispersion, coat the dispersion on the surface of the carbon adhesive transition layer (the actual coating amount of Ketjen black powder is 40 mg / cm 2 ), and dry and cure in a vacuum drying oven at 100°C for 1 hour to obtain a Ketjen black powder layer.

[0091] (4) Fix the substrate coated with the Ketjen black powder layer on a sample disc, place it in a vacuum chamber with a vacuum degree of 5*10 -4 Pa, and deposit a CoCrFeMnNi (Zhongnuoxinxin Technology (Beijing) Co., Ltd., Fe213863, φ50.8*5 mm) high-entropy alloy coating with an equimolar atomic ratio composition in a non-equilibrium magnetron sputtering deposition system. During the coating deposition process, set the Ar flow rate to 30 sccm, adjust the opening degree of the gate valve to control the working pressure to 10%, the resistance gauge working pressure to 0.5 Pa, and the film gauge working pressure to 2.0 Pa; connect the CoCrFeMnNi target material to the direct current power supply, set the sputtering power to 100 W, the substrate bias to -80 V, and the deposition time to 120 minutes. After the coating deposition is completed, close the film gauge protection valve, the direct current and bias power supply, and cool the sample in the vacuum chamber with the furnace to obtain a 304ss substrate with a Ketjen black-loaded high-entropy alloy corrosion-resistant coating on the surface.

[0092] The microstructure of the Ketjen black-loaded high-entropy alloy corrosion-resistant coating prepared in this embodiment was characterized by scanning electron microscopy, and the results are shown in Figure 1 From Figure 1 it can be seen that the coating surface has a three-dimensional network branched overall architecture and a surface pellet-like particle morphology.

[0093] The electrochemical performance of the Ketjenblack loaded high-entropy alloy corrosion resistant coating prepared in this example was measured in a three-electrode system flat plate electrolytic cell, with a Ag / AgCl reference electrode, a Pt mesh counter electrode, and the coating sample as the working electrode. The composite coating had a corrosion potential of 0.05 V and a corrosion current density of 5 x 10 -6 A / cm 2 in a 3.5 wt.% NaCl solution, which effectively protected the substrate.

[0094] Example 2

[0095] (1) Surface treatment of the substrate: The 304ss substrate was polished to a mirror finish using sandpaper of different grits, and the surface roughness was 1.3 nm. The polished 304ss substrate was ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 20 minutes, respectively, to remove grease and impurities on the surface of the substrate.

[0096] (2) A 0.3 mm thick carbon adhesive transition layer was adhered to the surface of the 304ss substrate.

[0097] (3) Ketjenblack powder (Ketjenblack EC-300J, apparent bulk density 125 kg / m 3 , particle size 45 μm) was dispersed in methanol at a concentration of 5 wt.% to obtain a dispersion, which was coated on the surface of the carbon adhesive transition layer (the actual coating amount of Ketjenblack powder was 30 mg / cm 2 ). After drying and curing in a vacuum drying oven at 100°C for 1 hour, a Ketjenblack powder layer was obtained.

[0098] (4) The substrate coated with the Ketjenblack powder layer was fixed on a sample disc and placed in a vacuum chamber with a vacuum degree less than 5 x 10 -4 Pa. An equimolar atomic ratio CoCrFeMnNi high-entropy alloy coating was deposited in a non-equilibrium magnetron sputtering deposition system. During the coating deposition process, the Ar flow rate was set to 25 sccm, the gate valve opening degree for adjusting and controlling the working pressure was set to 11%, the resistance gauge working pressure was 0.4 Pa, and the film gauge working pressure was 1.6 Pa. The CoCrFeMnNi target was connected to a direct current power supply, and the sputtering power was set to 110 W, the substrate bias was -90 V, and the deposition time was 130 minutes. After the coating deposition was completed, the film gauge protection valve, the direct current power supply, and the bias power supply were turned off, and the sample was cooled in the vacuum chamber with the furnace to obtain a 304ss substrate with a Ketjenblack loaded high-entropy alloy corrosion resistant coating on the surface.

[0099] The Ketjenblack loaded high-entropy alloy corrosion resistant coating prepared in this example was subjected to X-ray photoelectron spectroscopy analysis, and the XPS spectrum is shown in Figure 2 . As shown in Figure 2It can be seen from the Raman spectrum that C-O bond, C=O bond and Me-O (Me=Co, Cr, Fe, Mn, Ni) bond are formed at the interface between Ketjen black coating layer and CoCrFeMnNi deposition layer, which proves that a chemical bonding network containing metal-oxygen-carbon (Me-O-C) interaction is formed at the interface. The existence of the chemical bonding transition layer realizes the strong interface bonding between the coating layers.

[0100] Figure 3 The Raman spectrum of the Ketjen black loaded high-entropy alloy corrosion resistant coating prepared in this example is shown in the figure, from which the simultaneous existence of C-O bond and Me-O bond can be seen, which again proves the existence of the chemical bonding transition layer between the Ketjen black layer and the CoCrFeMnNi layer.

[0101] (5) The electrochemical performance of the composite coating was tested in a three-electrode system flat plate electrolytic cell, in which the reference electrode was Ag / AgCl, the counter electrode was Pt mesh, and the working electrode was the coating sample to be tested. The composite coating had a corrosion potential of 0.1 V and a corrosion current density of 5×10 -7 A / cm 2 in a 3.5wt.% NaCl solution, which could effectively protect the substrate.

[0102] Example 3

[0103] (1) Surface treatment of the substrate: polish the 304ss substrate with sandpaper of different grits and polish to mirror effect, with a surface roughness of 1.4 nm. Ultrasonically clean the polished 304ss substrate in acetone, anhydrous ethanol and deionized water for 10 minutes respectively to remove oil and impurities on the surface of the substrate.

[0104] (2) Adhere a carbon adhesive transition layer with a thickness of 0.4 mm on the surface of the 304ss substrate.

[0105] (3) Disperse Ketjen black powder (Ketjenblack EC-300J, apparent bulk density 140 kg / m 3 , particle size 46 μm) in methanol at a concentration of 5wt.% to obtain a dispersion, coat the dispersion on the surface of the carbon adhesive transition layer (the actual coating amount of Ketjen black powder is 35 mg / cm 2 ), and dry and cure in a vacuum drying oven at 100°C for 1 hour to obtain a Ketjen black powder layer.

[0106] (4) Fix the substrate coated with the Ketjen black powder layer on a sample disc and place it in a vacuum degree less than 5×10 -4A layer of CoCrFeMnNi high-entropy alloy coating with equal atomic ratio of components was deposited in a non-equilibrium magnetron sputtering deposition system in a vacuum chamber of Pa, during the deposition process, the Ar flow rate was set to 20 sccm, the gate valve opening degree for adjusting and controlling the working pressure was adjusted to 15%, the resistance gauge working pressure was 0.3 Pa, and the film gauge working pressure was 1.0 Pa; the CoCrFeMnNi target was connected to a direct current power supply, and the sputtering power was set to 120 W, the substrate bias voltage was -100 V, and the deposition time was 140 minutes. After the coating deposition was completed, the film gauge protection valve, the direct current power supply and the bias voltage power supply were turned off, and the sample was cooled in the vacuum chamber with the furnace to obtain a 304ss substrate with a surface having a Korich black loaded high-entropy alloy corrosion resistant coating.

[0107] Comparative Example 1

[0108] The difference from Example 1 is only that no CoCrFeMnNi coating was deposited, denoted as 304ss / C / KB.

[0109] Comparative Example 2

[0110] The difference from Example 1 is only that a carbon adhesive layer was adhered to the surface of the 304ss substrate and a CoCrFeMnNi coating was deposited, and no Korich black powder layer was coated, denoted as 304ss / C / CoCrFeMnNi.

[0111] The electrochemical performance of the 304ss substrates with the composite coating prepared in Example 3, Comparative Example 1 and Comparative Example 2 and the 304ss substrate without the coating were tested in a three-electrode system flat plate electrolytic cell, wherein the reference electrode was Ag / AgCl, the counter electrode was Pt mesh, and the working electrode was the sample to be tested. The test results are shown in Table 1. Figure 4 As shown in Table 1, the composite coating prepared in Example 3 (denoted as 304ss / C / KB / CoCrFeMnNi) has a corrosion potential of 0.01 V and a corrosion current density of 1 x 10 -6 A / cm 2 in a 3.5 wt.% NaCl solution; the composite coating in Comparative Example 1 in which only a carbon adhesive layer was adhered to the 304ss substrate and a Korich black powder coating was coated without depositing a CoCrFeMnNi coating (304ss / C / KB) has a corrosion potential of -0.1 V and a corrosion current density of 5 x 10 -7 A / cm 2 in a 3.5 wt.% NaCl solution; and the composite coating in Comparative Example 2 in which only a carbon adhesive layer was adhered to the 304ss substrate and a CoCrFeMnNi coating was deposited (304ss / C / CoCrFeMnNi) has a corrosion potential of -0.2 V and a corrosion current density of 6 x 10 -7 A / cm 2The corrosion current density. By comparison, it is concluded that the composite coating 304ss / C / KB / CoCrFeMnNi has relatively optimal comprehensive corrosion resistance, i.e. relatively higher corrosion potential and lower corrosion current density, and meanwhile the contribution of the KB layer and the CoCrFeMnNi layer to the corrosion resistance is respectively confirmed, i.e. the superimposed contribution of the two to the composite coating. Meanwhile, compared with the 304ss substrate without coating, it can be seen that the introduction of the coating realizes effective protection of the 304ss substrate, the corrosion potential is significantly improved, and the corrosion current density is reduced.

[0112] Since the substrate needs to be conductive in the electrochemical test, the 304ss substrate is only used in Examples 1-3 and Comparative Examples 1-2, and the preparation of the coating described in the present application is not limited to the 304ss substrate.

[0113] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A method for preparing a Koronens black loaded high-entropy alloy anticorrosion coating, characterized in that, The method comprises the following steps: 1) applying a carbon glue transition layer on the surface of the substrate material after pretreatment of the surface of the substrate material; 2) applying a carbon black layer on the surface of the carbon glue transition layer after mixing carbon black powder with methanol; 3) depositing a CoCrFeMnNi high-entropy alloy coating on the surface of the carbon black layer by magnetron sputtering to obtain a carbon black loaded high-entropy alloy corrosion resistant coating.

2. The preparation method of the Korichnei loaded high-entropy alloy anticorrosion coating according to claim 1, characterized in that, The substrate material in step 1) can be one of a polymer film, a paper-based material, a metal foil, and a graphene material. The pretreatment comprises grinding, polishing, and ultrasonic cleaning. The roughness of the surface of the substrate after the pretreatment is 1-2 nm.

3. The preparation method of the Korichnei loaded high-entropy alloy anticorrosion coating according to claim 2, characterized in that, The carbon glue in step 1) is made of a carbon-containing base polymer and nano-carbon fillers. The thickness of the carbon glue transition layer is 0.1-0.5 mm.

4. The preparation method of the Korichnei loaded high-entropy alloy anticorrosion coating according to claim 3, characterized in that, The apparent bulk density of the Ketjen black powder in step 2) is 125-145 kg / m 3 ; The particle size of the carbon black powder is 44-50 μm. The oil absorption value of the carbon black powder is 310-345 mL / 100 g. The sand content of the carbon black powder is ≤30 mg / kg. The moisture content of the carbon black powder is ≤0.5%. The volatile matter content of the carbon black powder is ≤1%. The iodine adsorption value of the carbon black powder is 780-840 mg / g. The ash content of the carbon black powder is ≤0.05%. The specific surface area of the ketjen black powder is 780-840 m 2 / g; The specific resistance of the carbon black powder is 0.5-2 Ω·cm. The pH value of the carbon black powder is 8-10. The coating amount of the ketjen black powder is 20 to 50 mg / cm 2 .

5. The preparation method of the Korich black loaded high-entropy alloy anticorrosion coating according to any one of claims 1-4, characterized in that, The parameters of the magnetron sputtering method in step 3) are as follows: The system is a non-equilibrium magnetron sputtering deposition system. Vacuum ≤ 5 x 10 -4 Pa; Argon gas is continuously supplied during the magnetron sputtering at a flow rate of 20-30 sccm. The opening degree of the gate valve for controlling the working pressure during the magnetron sputtering is 10-20%. The resistance gauge working pressure is 0.3-0.5 Pa. The film gauge working pressure is 1.0-2.0 Pa. The magnetron sputtering power is 100-120 W. The substrate bias voltage is -100 to -80 V. The deposition time is 100-140 min.

6. The preparation method of the Korichnei loaded high-entropy alloy anticorrosion coating according to claim 5, characterized in that, The CoCrFeMnNi high-entropy alloy coating in step 3) has an equimolar atomic ratio.

7. A carbon black loaded high-entropy alloy corrosion resistant coating prepared by the method of any one of claims 1-6.

8. The method of any one of claims 1-6 and the carbon black loaded high-entropy alloy corrosion resistant coating of claim 7 for use in sensors.

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