A high-entropy alloy nanoparticle for inhibiting microbial corrosion and its preparation method

Abstract

The present invention provides a high-entropy alloy nanoparticle for inhibiting microbial corrosion and a preparation method thereof, belonging to the technical field of microbial corrosion and protection. The high-entropy alloy nanoparticle for inhibiting microbial corrosion has a chemical general formula of FeCoNiT ix Cu y , wherein the molar ratio of Fe, Co, and Ni is 1:1:1, the molar ratio of Ti to Fe is equal to x, and the molar ratio of Cu to Fe is equal to y, where 1.0 < x ≤ 1.5 and 0 < y ≤ 2. The preparation method of the present invention is simple and easy to operate, and the elemental powder of each metal element in the alloy composition can achieve a high conversion rate; the reaction raw materials are widely sourced and abundantly supplied; the supporting equipment has a low cost, meeting the requirements of large-scale industrial production. The high-entropy alloy nanoparticle of the present invention can significantly reduce the corrosion current density of the material, obtain a high corrosion inhibition rate, effectively inhibit the microbial corrosion of the material, and overcome the problem that many microbial corrosion inhibitors are prone to cause drug resistance in microorganisms. At the same time, supplemented by sunlight irradiation, the synergistic effect inhibits microbial corrosion.

Description

Technical Field

[0001] The invention belongs to the technical field of microbial corrosion and protection, and specifically relates to high entropy alloy nanoparticles that inhibit microbial corrosion and a preparation method thereof. Background Art

[0002] Microbiologically influenced corrosion (MIC) refers to the process in which the corrosion and degradation of the material surface is directly or indirectly caused by the life activities of microorganisms. According to statistics, the economic losses caused by MIC have exceeded 2.7 trillion US dollars each year. MIC not only causes material failure and economic losses, but also leads to major safety accidents. In order to solve the problem of MIC of materials, various strategies to inhibit MIC have been reported, such as material selection and modification, electrochemical protection, corrosion inhibitors and antibacterial agents, anticorrosion coatings, etc.

[0003] At present, microbial corrosion inhibitors have attracted extensive attention due to their high efficiency in inhibiting microbial growth, wide application range and multiple synergistic mechanisms. However, most existing microbial corrosion inhibitors have problems such as short inhibition time, poor stability and drug resistance of microorganisms, which make it impossible to achieve long-term, stable and high-efficiency inhibition of microbial corrosion of materials.

[0004] High entropy alloys have excellent stability and corrosion resistance due to their unique structure and composition, and have become a research hotspot. When they are refined to nanometer size, high entropy alloy nanoparticles will have the characteristics of large specific surface area, high reactivity and multifunctional design, showing great potential in reducing microbial activity and inhibiting microbial corrosion. d High entropy alloy nanoparticles of transition metal elements can be enhanced by dd The inter-band transition improves its absorption performance in the solar spectrum, showing excellent photothermal conversion ability. The photothermal conversion can be used under solar irradiation to further improve the microbial corrosion inhibition rate. As a stable and efficient method for inhibiting microbial corrosion, it has broad application prospects. Summary of the invention

[0005] In order to overcome the shortcomings of existing microbial corrosion inhibitors, the present invention provides a high entropy alloy nanoparticle for inhibiting microbial corrosion and a preparation method thereof. The high entropy alloy nanoparticles prepared by the method can effectively inhibit microbial growth and microbial corrosion of materials, and at the same time, the microbial corrosion inhibition performance of the high entropy alloy nanoparticles is further improved under solar irradiation.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] The present invention provides a high entropy alloy nanoparticle that inhibits microbial corrosion, and its general chemical formula is FeCoNiTi x Cu y , wherein the molar ratio of Fe, Co and Ni is 1:1:1, the molar ratio of Ti to Fe is equal to x, the molar ratio of Cu to Fe is equal to y, 1.0<x≤1.5, 0<y≤2.

[0008] Furthermore, the crystal phase structure of the high entropy alloy nanoparticles is a single solid solution.

[0009] Furthermore, the particle size of the high entropy alloy nanoparticles ranges from 5nm to 200nm.

[0010] The present invention also provides a method for preparing high entropy alloy nanoparticles for inhibiting microbial corrosion, comprising the following steps:

[0011] (1) Precursor preparation: The metal powder raw materials of Fe, Co, Ni, Ti and Cu are uniformly mixed according to the proportion and pressed into metal flakes;

[0012] (2) DC plasma arc furnace method: The metal flakes prepared in step (1) are placed in a DC arc plasma discharge device, vacuumized, and arc discharge is ignited in a mixed atmosphere of reaction gas and protective gas to evaporate the metal flakes. The metal flakes are then cooled and allowed to stand for passivation to obtain high entropy alloy nanoparticles that inhibit microbial corrosion.

[0013] Furthermore, in step (1), the metal element raw material is a metal powder with a purity of ≥99.5% and an average particle size of 40 μm-50 μm;

[0014] Optionally, in step (1), a tablet press is used to press the metal single substance powders of Fe, Co, Ni, Ti and Cu into metal flakes at a pressure of 15 MPa-25 MPa.

[0015] Furthermore, in step (2), the volume ratio of the reaction gas to the protective gas is (2-8):1;

[0016] The reaction gas is hydrogen, and the protective gas is one or more mixed gases of nitrogen, helium, neon and argon.

[0017] Furthermore, in step (2), the control current of the discharge process is 180A-240A, the voltage is 20V-30V, and the discharge duration is 10min-25min; condensate is used for cooling, and the static passivation time is 6h-8.5h.

[0018] The invention provides an application of high entropy alloy nanoparticles for inhibiting microbial corrosion, which is used in the field of inhibiting microbial corrosion.

[0019] Furthermore, the application of the high entropy alloy nanoparticles for inhibiting microbial corrosion can dissolve copper ions, and then assisted by sunlight irradiation, synergistically inhibit microbial corrosion;

[0020] Furthermore, the microorganisms suitable for inhibiting microbial corrosion performance include one or more of Pseudomonas aeruginosa, Bacillus vietnamiensis, Shewanella and sulfate-reducing bacteria.

[0021] Furthermore, the application of the high entropy alloy nanoparticles for inhibiting microbial corrosion is used to inhibit microbial corrosion in marine engineering equipment. 400 μg / mL of high entropy alloy nanoparticles for inhibiting microbial corrosion are added to a 2216E liquid culture medium containing 1% Pseudomonas aeruginosa bacterial solution, and the 304 stainless steel sample is immersed in a 30°C incubator for 7 days. The corrosion inhibition rate reaches 97.51%. Further, a standard sunlight (1 kW / m 2 ) irradiation and immersion in a 30℃ incubator for 7 days, the corrosion inhibition rate reached 98.04%.

[0022] The beneficial effects of the present invention are as follows:

[0023] The preparation method is simple and easy to operate, and the metal element powders of the alloy composition can achieve a high conversion rate; the reaction raw materials are widely available and in sufficient supply; the supporting equipment is low in cost, which meets the needs of large-scale industrial production. According to tests, the high-entropy alloy nanoparticles prepared by the present invention can significantly reduce the corrosion current density of the material, obtain a high corrosion inhibition rate, and effectively inhibit the microbial corrosion of the material, overcoming the problem that many microbial corrosion inhibitors easily cause microorganisms to develop drug resistance. At the same time, with the help of sunlight irradiation, its microbial corrosion inhibition performance is further improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 FeCoNiTi prepared in Example 1 1.2 Cu 1.0 X-ray diffraction (XRD) pattern of high entropy alloy nanoparticles;

[0025] Figure 2 FeCoNiTi prepared in Example 1 1.2 Cu 1.0 Transmission electron microscopy (TEM) image of high entropy alloy nanoparticles;

[0026] Figure 3 FeCoNiTi prepared in Example 1 1.2 Cu 1.0 Particle size statistics of high entropy alloy nanoparticles;

[0027] Figure 4FeCoNiTi prepared in Example 1 1.2 Cu 1.0 TEM-EDS element distribution map of high entropy alloy nanoparticles;

[0028] Figure 5 FeCoNiTi prepared in Example 1 1.2 Cu 1.0 UV-visible-near-infrared absorption spectra of high-entropy alloy nanoparticles;

[0029] Figure 6 FeCoNiTi prepared in Example 1 1.2 Cu 1.0 Temperature variation of high entropy alloy nanoparticles under 1 standard sun irradiation;

[0030] Figure 7 FeCoNiTi prepared in Example 2 1.4 Cu 2.0 X-ray diffraction (XRD) pattern of high entropy alloy nanoparticles;

[0031] Figure 8 FeCoNiTi prepared in Example 2 1.4 Cu 2.0 Statistical diagram of particle size distribution of high entropy alloy nanoparticles;

[0032] Fig. 9 FeCoNiTi prepared in Example 2 1.4 Cu 2.0 TEM-EDS element distribution map of high entropy alloy nanoparticles;

[0033] Fig.10 FeCoNiTi prepared in Example 2 1.4 Cu 2.0 UV-visible-near-infrared absorption spectra of high-entropy alloy nanoparticles;

[0034] Fig.11 FeCoNiTi prepared in Example 3 1.5 Cu 0.25 X-ray diffraction (XRD) pattern of high entropy alloy nanoparticles;

[0035] Fig.12 FeCoNiTi prepared in Example 3 1.5 Cu 0.25 Particle size statistics of high entropy alloy nanoparticles;

[0036] Fig.13 FeCoNiTi prepared in Example 3 1.5 Cu 0.25 TEM-EDS element distribution map of high entropy alloy nanoparticles;

[0037] Fig.14 FeCoNiTi prepared in Example 3 1.5 Cu 0.25 UV-visible-near-infrared absorption spectra of high-entropy alloy nanoparticles;

[0038] Fig.15 FeCoNiTi prepared in Comparative Example 1 1.3 X-ray diffraction (XRD) pattern of high entropy alloy nanoparticles;

[0039] Fig.16 FeCoNiTi prepared in Comparative Example 1 1.3 Particle size statistics of high entropy alloy nanoparticles;

[0040] Fig.17 FeCoNiTi prepared in Comparative Example 1 1.3 TEM-EDS element distribution map of high entropy alloy nanoparticles;

[0041] Fig.18 Figure 1 is a pitting morphology of the surface of the 304 stainless steel sample in Application Example 1, wherein Figure (a) is a pitting morphology of the surface of the 304 stainless steel in the co-immersion culture medium system without the addition of the high entropy alloy nanoparticles of Example 1, and Figure (b) is a pitting morphology of the surface of the 304 stainless steel in the co-immersion culture medium system with the addition of the high entropy alloy nanoparticles of Example 1;

[0042] Fig.19 Figure 2 is a pitting corrosion morphology of the surface of the 304 stainless steel sample in Application Example 2, wherein Figure (a) is a pitting corrosion morphology of the surface of the 304 stainless steel in the co-immersion culture medium system without the addition of the high entropy alloy nanoparticles of Example 1 under the condition of applying sunlight, and Figure (b) is a pitting corrosion morphology of the surface of the 304 stainless steel in the co-immersion culture medium system with the addition of the high entropy alloy nanoparticles of Example 1 under the condition of applying sunlight. DETAILED DESCRIPTION

[0043] The following is a further detailed description of a high entropy alloy nanoparticle for inhibiting microbial corrosion provided by the present invention and its preparation method and application in conjunction with specific embodiments and drawings. To avoid experimental errors and contingencies, the quantitative experiments performed in the following embodiments were repeated three times or more.

[0044] The high entropy alloy nanoparticles of the present invention can dissolve copper ions and produce irreversible thermal damage to microorganisms under sunlight irradiation, thereby playing a synergistic role in inhibiting microbial corrosion.

[0045] The bacteria species causing microbial corrosion used in this embodiment is Pseudomonas aeruginosa.

[0046] Example 1

[0047] A method for preparing high entropy alloy nanoparticles for inhibiting microbial corrosion comprises the following steps:

[0048] (1) Precursor preparation: Fe, Co, Ni, Ti and Cu metal powders with a purity of 99.8% and an average particle size of 45 μm were weighed and prepared according to the nominal composition of FeCoNiTi 1.2 Cu 1.0 Prepare 10 g of the mixture, mix it evenly, and use a tablet press to press the powder into metal flakes with a diameter of 10 mm at 20 MPa.

[0049] (2) DC plasma arc furnace method: Place the metal sheet from step (1) in a DC arc plasma discharge device as the anode and a tungsten electrode as the cathode, and evacuate to 1.2×10 -2 Pa, filled with hydrogen and argon, the volume of hydrogen is twice that of argon, and the total gas pressure is maintained at 1.0×10 4 Pa, ignite the arc, control the current and voltage at 180A and 25V respectively, evaporate the metal sheet, discharge reaction for 10min, and at the same time fill in condensed water and let it stand for passivation for 6.5h to obtain high entropy alloy nanoparticles that inhibit microbial corrosion.

[0050] Results Characterization

[0051] like Figure 1 The XRD spectrum of the high entropy alloy nanoparticles for inhibiting microbial corrosion in this embodiment is shown, which is a simple solid solution structure; the calculated mixing entropy is 13.38 J / mol / K (>1.5R); Figure 2 The TEM image is shown, indicating that the high entropy alloy is a nanoparticle; Figure 3 The particle size distribution statistics are shown in FIG. 1 , which shows that the particle size of the high entropy alloy nanoparticles is 10 nm-70 nm, and the average particle size is 23.84 nm. Figure 4 The TEM-EDS element distribution diagram is shown, indicating that the elements of the high entropy alloy nanoparticles are uniformly miscible; Figure 5 The ultraviolet-visible-near-infrared absorption spectrum shows that the average absorption rate of the high-entropy alloy nanoparticles in the entire solar spectrum (250nm-2500nm) is about 97%; Figure 6 In a standard sunlight (1kW / m 2 ) surface temperature change of high entropy alloy nanoparticles under irradiation, and the results show that it has excellent photothermal conversion performance.

[0052] Example 2

[0053] A method for preparing high entropy alloy nanoparticles for inhibiting microbial corrosion comprises the following steps:

[0054] (1) Precursor preparation: Fe, Co, Ni, Ti and Cu metal powders with a purity of 99.5% (average particle size of 40 μm) were weighed and prepared according to the nominal composition of FeCoNiTi 1.4 Cu 2.0 Prepare 10 g, mix evenly, and use a tablet press to press the powder into metal flakes with a diameter of 10 mm at 15 MPa.

[0055] (2) DC plasma arc furnace method: Place the metal sheet from step (1) in a DC arc plasma discharge device as the anode and a tungsten electrode as the cathode, and evacuate to 1.2×10 -2 Pa, filled with hydrogen and nitrogen, the volume of hydrogen is 6 times that of nitrogen, and the total pressure is maintained at 1.0×10 4 Pa, ignite the arc, control the current and voltage at 210A and 30V respectively, evaporate the metal sheet, discharge reaction for 25min, and at the same time fill in condensed water and let it stand for passivation for 8.5h to obtain high entropy alloy nanoparticles that inhibit microbial corrosion.

[0056] Results Characterization

[0057] like Figure 7 The XRD spectrum of the high entropy alloy nanoparticles for inhibiting microbial corrosion in this embodiment is shown, which is a simple solid solution structure; the calculated mixing entropy is 12.98 J / mol / K (>1.5R); Figure 8 The particle size distribution is shown in the figure, which shows that the particle size of the high entropy alloy nanoparticles is 40nm-160nm, and the average particle size is 99.53nm; Fig. 9 The TEM-EDS element distribution diagram is shown, indicating that the elements of the high entropy alloy nanoparticles are uniformly miscible; Fig.10 The ultraviolet-visible-near-infrared absorption spectrum shows that the average absorption rate of the high-entropy alloy nanoparticles in the entire solar spectrum (250nm-2500nm) is about 92%.

[0058] Example 3

[0059] A method for preparing high entropy alloy nanoparticles for inhibiting microbial corrosion comprises the following steps:

[0060] (1) Precursor preparation: Fe, Co, Ni, Ti and Cu metal powders with a purity of 99.6% (average particle size of 50 μm) were weighed and prepared according to the nominal composition of FeCoNiTi 1.5 Cu 0.25 10 g was prepared and after uniform mixing, the powder was pressed into metal flakes with a diameter of 10 mm using a tablet press at 25 MPa.

[0061] (2) DC plasma arc furnace method: Place the metal sheet from step (1) in a DC arc plasma discharge device as the anode and a tungsten electrode as the cathode, and evacuate to 1.2×10 -2 Pa, filled with hydrogen and neon, the volume of hydrogen is 8 times that of neon, and the total gas pressure is maintained at 1.0×10 4 Pa, ignite the arc, control the current and voltage at 240A and 20V respectively, evaporate the metal sheet, discharge reaction for 15min, and at the same time fill in condensed water and let it stand for passivation for 6h to obtain high entropy alloy nanoparticles that inhibit microbial corrosion.

[0062] Results Characterization

[0063] like Fig.11 The XRD spectrum of the high entropy alloy nanoparticles for inhibiting microbial corrosion in this embodiment is shown, which is a simple solid solution structure; the calculated mixing entropy is 12.71 J / mol / K (>1.5R); Fig.12 The particle size distribution statistics are shown in FIG. 1 , which shows that the particle size of the high entropy alloy nanoparticles is 5 nm-180 nm, and the average particle size is 59.80 nm. Fig.13 The TEM-EDS element distribution diagram is shown, indicating that the elements of the high entropy alloy nanoparticles are uniformly miscible; Fig.14 The ultraviolet-visible-near-infrared absorption spectrum shows that the average absorption rate of the high-entropy alloy nanoparticles in the entire solar spectrum (250nm-2500nm) is about 97%.

[0064] Comparative Example 1

[0065] A method for preparing alloy nanoparticles comprises the following steps:

[0066] (1) Precursor preparation: Fe, Co, Ni, and Ti metal powders with a purity of 99.8% (average particle size of 45 μm) were weighed and prepared according to the nominal composition of FeCoNiTi 1.3 Prepare 10 g; after uniform mixing, use a tablet press to press the powder into a metal sheet with a diameter of 10 mm at 20 MPa.

[0067] (2) Arc Melting: Place the metal sheet in a DC arc plasma discharge device as the anode, and the tungsten electrode as the cathode, and evacuate to 1.2×10 -2 Pa, filled with hydrogen and argon, the volume of hydrogen is 3 times that of argon, and the total gas pressure is maintained at 1.5×10 4 Pa, ignite the arc, control the current and voltage at 200A and 20V respectively, evaporate the metal sheet, discharge reaction for 15min, fill with condensed water and let it stand for passivation for 8h to obtain FeCoNiTi 1.3 Alloy nanoparticles.

[0068] like Fig.15The XRD pattern of the alloy nanoparticles in this comparative example is shown, which is a simple solid solution structure; the mixing entropy is calculated to be 11.53 J / mol / K (<1.5R); Fig.16 The particle size distribution is shown in the figure, which shows that the particle size of the alloy nanoparticles is 5nm-140nm, and the average particle size is 43.50nm; Fig.17 The TEM-EDS element distribution diagram is shown, indicating that the elements of the alloy nanoparticles are uniformly miscible.

[0069] Application Example 1

[0070] The high entropy alloy nanoparticles for inhibiting microbial corrosion prepared in Example 1 were used to inhibit microbial corrosion. The corrosive material was 304 stainless steel, and the microorganism was Pseudomonas aeruginosa, which is common in nature.

[0071] The corrosion material sample used in this application example is 304 stainless steel, and its composition and mass percentage are: C0.08%, Mn 2.00%, P 0.045%, S 0.030%, Si 1.01%, Cr 19.00%, Ni 9.35%, Fe is the balance; the sample size is: 10mm×10mm×3mm;

[0072] In this application example, 2216E culture medium is used, and its composition is 19.45g / L NaCl, 5.98g / L MgCl2, 3.24g / LNa2SO4, 1.8g / L CaCl2, 0.55g / L KCl, 0.16g / L Na2CO3, 0.08g / L KBr, 0.034g / L SrCl2, 0.08g / L SrBr2, 0.022g / L H3BO3, 0.004g / L NaSiO3, 0.0024g / L NaF, 0.0016g / L NH4NO3, 0.008g / L NaH2PO4, 5.0g / L peptone, 1.0g / L yeast extract, and 0.1g / L ferric citrate.

[0073] Corrosion Inhibition Performance Analysis of High Entropy Alloy Nanoparticles for Microbial Inhibition

[0074] (1) Electrochemical analysis of the inhibitory effect of high entropy alloy nanoparticles on microbial corrosion

[0075] The 304 stainless steel sample was mounted as the working electrode and FeCoNiTi 1.2 Cu 1.0High entropy alloy nanoparticles were added into 2216E liquid culture medium containing 1% Pseudomonas aeruginosa bacterial solution until the concentration of nanoparticles reached 400 μg / mL as the experimental group, and 2216E liquid culture medium containing 1% Pseudomonas aeruginosa bacterial solution without nanoparticles was used as the control group; the same 304 stainless steel working electrode was immersed in both the experimental group and the control group for 7 days, and the electrochemical test adopted a standard three-electrode system. The open circuit potential (OCP), linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curve (PPC) of all samples were tested by electrochemical workstation.

[0076] According to the potentiodynamic polarization curve, the corrosion current density of the 304 stainless steel working electrode was obtained by Tafel analysis and fitting. i corr ), compared with the control group, the corrosion current density of the experimental group increased from 164.6nA / cm 2 ( i corr ) dropped to 4.1nA / cm 2 ( i' corr ), its corrosion inhibition rate is 97.51%, and the corrosion inhibition rate calculation formula is as follows:

[0077]

[0078] The electrochemical test results show that the FeCoNiTi 1.2 Cu 1.0 High entropy alloy nanoparticles have excellent microbial corrosion inhibition effect.

[0079] (2) Corrosion morphology characterization of high entropy alloy nanoparticles' performance in inhibiting microbial corrosion

[0080] The 304 stainless steel sample was placed in a 2216E liquid culture medium containing 1% Pseudomonas aeruginosa bacterial solution, and FeCoNiTi with a concentration of 400 μg / mL was added. 1.2 Cu 1.0 High entropy alloy nanoparticles were used as the experimental group, and no high entropy alloy nanoparticles were added to the control group. The two co-immersion culture medium systems were placed in a 30°C incubator and immersed for 7 days. After immersion for 7 days, the biofilm and corrosion products were removed, and the corrosion morphology was observed by laser scanning confocal electron microscopy. Fig.18As shown, when no high entropy alloy nanoparticles are added, the depth of the corrosion pit of the sample is much greater than the depth of the pit of the sample with nanoparticles added.

[0081] Application Example 2

[0082] The high entropy alloy nanoparticles for inhibiting microbial corrosion prepared in Example 1 were used to inhibit microbial corrosion, and assisted by sunlight irradiation. The corrosive material was 304 stainless steel, and the microorganism was Pseudomonas aeruginosa, which is common in nature.

[0083] The corrosion material sample used in this application example is 304 stainless steel, and its composition and mass percentage are: C0.08%, Mn 2.00%, P 0.045%, S 0.030%, Si 1.01%, Cr 19.00%, Ni 9.35%, Fe is the balance; the sample size is: 10mm×10mm×3mm;

[0084] In this application example, 2216E culture medium is used, and its composition is 19.45g / L NaCl, 5.98g / L MgCl2, 3.24g / LNa2SO4, 1.8g / L CaCl2, 0.55g / L KCl, 0.16g / L Na2CO3, 0.08g / L KBr, 0.034g / L SrCl2, 0.08g / L SrBr2, 0.022g / L H3BO3, 0.004g / L NaSiO3, 0.0024g / L NaF, 0.0016g / L NH4NO3, 0.008g / L NaH2PO4, 5.0g / L peptone, 1.0g / L yeast extract, and 0.1g / L ferric citrate;

[0085] Light intensity is 1kW / m 2 .

[0086] Analysis of the corrosion inhibition performance of high entropy alloy nanoparticles to inhibit microbial corrosion under sunlight irradiation

[0087] (1) Electrochemical analysis of the inhibitory effect of high entropy alloy nanoparticles on microbial corrosion

[0088] The culture medium, culture temperature, culture time, working electrode and microbial corrosion inhibitor used in this example are the same as those in Example 1. The samples were subjected to electrochemical analysis, and the electrochemical tests all adopted a standard three-electrode system. 1.2 Cu 1.0 The high entropy alloy nanoparticles were 400 μg / mL in 2216E medium supplemented with simulated sunlight (1 kW / m 2 ) irradiation as the experimental group, and the control group did not add FeCoNiTi 1.2 Cu1.0 High entropy alloy nanoparticles were immersed in the experimental group and the control group for 7 days. The FeCoNiTi 1.2 Cu 1.0 The microbial corrosion inhibition performance of high entropy alloy nanoparticles was tested, including open circuit potential, linear polarization resistance and other data; compared with the control group, the linear polarization resistance of the experimental group was much greater than that of the control group; the corrosion current density of the experimental group increased from 148.2nA / cm 2 ( i corr ) dropped to 2.9nA / cm 2 ( i' corr ), the corrosion inhibition rate is 98.04% (calculated using the corrosion inhibition rate formula in Application Example 1). The results show that after applying sunlight irradiation, FeCoNiTi 1.2 Cu 1.0 The corrosion resistance of high entropy alloy nanoparticles is further improved.

[0089] (2) Corrosion morphology characterization of high entropy alloy nanoparticles' performance in inhibiting microbial corrosion

[0090] The 304 stainless steel sample was placed in a 2216E liquid culture medium containing 1% Pseudomonas aeruginosa bacterial solution, and FeCoNiTi with a concentration of 400 μg / mL was added. 1.2 Cu 1.0 High entropy alloy nanoparticles were used as the experimental group, and no high entropy alloy nanoparticles were added to the control group. The two co-immersion culture medium systems were then placed in a 30°C incubator for 7 days. After 7 days of immersion, the biofilm and corrosion products on the sample surface were removed. The corrosion morphology of the sample surface was observed using a laser confocal scanning electron microscope. Fig.19 The pitting morphology of 304 stainless steel surface is shown. It is found that after adding high entropy alloy nanoparticles and irradiating with simulated sunlight, the surface of the sample is smooth and there is no obvious corrosion pit, which further verifies that FeCoNiTi 1.2 Cu 1.0 High entropy alloy nanoparticles can effectively inhibit microbial corrosion of materials.

[0091] Comparative application example 1

[0092] The alloy nanoparticles prepared in Comparative Example 1 were used to inhibit microbial corrosion, and the corrosion material samples 304 stainless steel and 2216E culture medium were the same as those in Application Example 1.

[0093] Inhibition of Microbial Corrosion of 304 Stainless Steel by Alloy Nanoparticles

[0094] (1) Electrochemical analysis of the performance of alloy nanoparticles in inhibiting microbial corrosion

[0095] The electrochemical test adopts a three-electrode system, and the working electrode is made of 304 stainless steel. Under aerobic conditions, the working electrode is immersed in the presence or absence of FeCoNiTi 1.3 The nanoparticles were added to a 2216E liquid culture medium containing 1% Pseudomonas aeruginosa culture medium at a concentration of 400 μg / mL. The group with added nanoparticles was used as the experimental group, and the group without added nanoparticles was used as the control group. The open circuit potential, linear polarization resistance, electrochemical impedance spectrum and potentiodynamic polarization curve of all samples were tested using an electrochemical workstation. According to the potentiodynamic polarization curve, the corrosion current density ( i corr Compared with the control group, the corrosion current density of the experimental group increased from 64.6nA / cm 2 ( i corr ) dropped to 34.9nA / cm 2 ( i' corr ), and its corrosion inhibition rate is 78.80% (calculated using the corrosion inhibition rate formula in Application Example 1); the electrochemical test results show that FeCoNiTi 1.3 Nanoparticles have a microbial corrosion inhibitory effect.

[0096] (2) Corrosion morphology characterization of alloy nanoparticles' performance in inhibiting microbial corrosion

[0097] The 304 stainless steel sample was placed in a solution containing 400 μg / mL FeCoNiTi 1.3 Nanoparticles and 1% Pseudomonas aeruginosa culture medium 2216E supplemented with simulated sunlight irradiation as the experimental group, without adding FeCoNiTi 1.3 High entropy alloy nanoparticles served as the control group. After 7 days of immersion, the biofilm and corrosion products on the sample surface were removed, and the corrosion morphology of the sample surface was observed using a laser confocal scanning electron microscope. It was found that after adding nanoparticles, the depth of the corrosion pits in the experimental group was reduced by 45% compared with the control group, further confirming that the addition of nanoparticles helps inhibit microbial corrosion of the material.

[0098] Comparative Application Example 2

[0099] The only difference from comparative application example 1 is that the microbial corrosion inhibition performance of 304 stainless steel is analyzed with the aid of sunlight irradiation.

[0100] Inhibition of Microbial Corrosion of 304 Stainless Steel by Alloy Nanoparticles Assisted by Sunlight Irradiation

[0101] (1) Electrochemical analysis of the performance of alloy nanoparticles in inhibiting microbial corrosion

[0102] The culture medium, culture temperature, culture time, working electrode and microbial corrosion inhibitor used in this embodiment are the same as those in Comparative Example 1. The samples were subjected to electrochemical analysis, and the working electrode was placed in a solution containing FeCoNiTi 1.3 Nanoparticles (400 μg / mL) and 1% Pseudomonas aeruginosa culture medium 2216E supplemented with simulated sunlight were used as the experimental group, and FeCoNiTi was not added to the control group. 1.3 Nanoparticles. FeCoNiTi was measured by electrochemical workstation 1.3 The microbial corrosion inhibition performance of the nanoparticles was tested, including open circuit potential, linear polarization resistance and other data; compared with the control group, the corrosion current density of the experimental group increased from 148.2nA / cm 2 ( i corr ) dropped to 19.3nA / cm 2 ( i' corr ), the corrosion inhibition rate was 86.98%. The results showed that after solar irradiation, FeCoNiTi 1.3 The corrosion resistance of nanoparticles is further improved.

[0103] (2) Corrosion morphology characterization of alloy nanoparticles' performance in inhibiting microbial corrosion

[0104] The 304 stainless steel sample was placed in a solution containing 400 μg / mL FeCoNiTi 1.3 Nanoparticles and 1% Pseudomonas aeruginosa culture medium 2216E supplemented with simulated sunlight irradiation were used as the experimental group, and FeCoNiTi was not added. 1.3 High entropy alloy nanoparticles served as the control group. After 7 days of immersion, the biofilm and corrosion products on the sample surface were removed. The corrosion morphology of the sample surface was observed using a laser confocal scanning electron microscope. It was found that after adding nanoparticles, the depth of the corrosion pits in the experimental group was reduced by 45% compared with the control group.

[0105] Through the analysis of the microbial corrosion inhibition performance in Application Example 1, Application Example 2 and Comparative Application Example 1 and Comparative Application Example 2, it can be seen that in the study of microbial corrosion inhibition of 304 stainless steel materials, the five elements (FeCoNiTi x Cu y ) high entropy alloy nanoparticles compared to quaternary (FeCoNiTi x) The inhibitory effect of the medium entropy alloy nanoparticles on microbial corrosion is significantly improved, further indicating that the dissolved copper ions have a good inhibitory effect on microbial corrosion; at the same time, the high entropy alloy nanoparticles of the present invention, supplemented by sunlight irradiation, can further enhance the inhibitory effect of microbial corrosion. In summary, the high entropy alloy nanoparticles for inhibiting microbial corrosion of the present invention have broad application prospects in the field of efficient inhibition of microbial corrosion.

Claims

1. A high entropy alloy nanoparticle for inhibiting microbial corrosion, characterized in that: The chemical formula of the high entropy alloy nanoparticles that inhibit microbial corrosion is FeCoNiTi x Cu y , wherein the molar ratio of Fe, Co and Ni is 1:1:1, the molar ratio of Ti to Fe is equal to x, the molar ratio of Cu to Fe is equal to y, 1.0<x≤1.5, 0<y≤2; the crystal phase structure of the high entropy alloy nanoparticles is a single solid solution; the particle size range of the high entropy alloy nanoparticles is 5nm-200nm.

2. The high entropy alloy nanoparticles for inhibiting microbial corrosion according to claim 1, characterized in that: The method for preparing the high entropy alloy nanoparticles comprises the following steps: (1) Precursor preparation: Fe, Co, Ni, Ti and Cu metal powder raw materials are uniformly mixed according to a proportion and pressed into metal flakes; (2) DC plasma arc furnace method: The metal flakes prepared in step (1) are placed in a DC arc plasma discharge device, vacuumized, and arc discharge is ignited in a mixed atmosphere of reaction gas and protective gas to evaporate the metal flakes, followed by cooling and static passivation treatment to obtain high entropy alloy nanoparticles that inhibit microbial corrosion.

3. The high entropy alloy nanoparticles for inhibiting microbial corrosion according to claim 2, characterized in that: In step (1) of the method for preparing high entropy alloy nanoparticles, the metal element raw material is a metal powder with a purity of ≥99.5% and a particle size of 40 μm-50 μm; Step (1) uses a tablet press to press metal single substance powders of Fe, Co, Ni, Ti and Cu into metal flakes at a pressure of 15 MPa-25 MPa.

4. The high entropy alloy nanoparticles for inhibiting microbial corrosion according to claim 2, characterized in that: In step (2) of the method for preparing high entropy alloy nanoparticles, the volume ratio of the reaction gas to the protective gas is (2-8):1; The reaction gas is hydrogen, and the protective gas is one or more mixed gases of nitrogen, helium, neon and argon.

5. The high entropy alloy nanoparticles for inhibiting microbial corrosion according to claim 2, characterized in that: In step (2) of the method for preparing high entropy alloy nanoparticles, the controlled current of the discharge process is 180A-240A, the voltage is 20V-30V, and the discharge duration is 10min-25min; condensate is used for cooling, and the static passivation time is 6h-8.5h.

6. The use of high entropy alloy nanoparticles for inhibiting microbial corrosion according to claim 1, characterized in that: Used in the field of inhibiting microbial corrosion.

7. The use of high entropy alloy nanoparticles for inhibiting microbial corrosion as claimed in claim 6, characterized in that: The high entropy alloy nanoparticles that inhibit microbial corrosion can dissolve copper ions, and when irradiated with sunlight, the synergistic effect inhibits microbial corrosion. The microorganisms suitable for inhibiting microbial corrosion performance include one or more of Pseudomonas aeruginosa, Bacillus vietnamiensis, Shewanella and sulfate-reducing bacteria.

8. The use of high entropy alloy nanoparticles for inhibiting microbial corrosion as claimed in claim 6, characterized in that: For inhibiting microbial corrosion in marine engineering equipment, 400 μg / mL of high-entropy alloy nanoparticles that inhibit microbial corrosion were added to a 2216E liquid culture medium containing 1% Pseudomonas aeruginosa, and then immersed in a 304 stainless steel sample and placed in a 30°C incubator for 7 days. The corrosion inhibition rate reached 97.51%. Further assisted by a standard sunlight of 1 kW / m 2 Under irradiation, the corrosion inhibition rate reached 98.04% after immersion in a 30℃ incubator for 7 days.

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