Method for preparing fabric with surface-loaded high-entropy alloy nanoparticles

Abstract

The present invention discloses a method for preparing a fabric surface-loaded with high-entropy alloy nanoparticles. The method comprises the following steps: sequentially washing the fabric material to remove impurities and subjecting it to a plasma treatment; mixing a liquid metal solution with a polymer solution to prepare a liquid metal / polymer mixed solution; coating the liquid metal / polymer mixed solution on the pretreated fabric surface to form a liquid metal-polymer mixed layer; dispersing the high-entropy alloy nanoparticles in a liquid medium, ultrasonically dispersing the particles, spraying the dispersion onto the fabric obtained in the previous step, and applying low-temperature pressurization to obtain the final product. The method can achieve good adhesion of the high-entropy alloy nanoparticles to the fabric, and, leveraging the antimicrobial elements and photothermal effects of the high-entropy alloy nanoparticles, imparts excellent antimicrobial properties to the fabric (or fiber). This method is simple to prepare and readily adaptable to industrial production.

Description

Technical Field

[0001] The invention belongs to the field of functional fabrics (fibers), and in particular relates to a method for preparing a fabric whose surface is loaded with high-entropy alloy nanoparticles. Background Art

[0002] Bacterial contact infections have always been a serious threat to human health. The global outbreak of the novel coronavirus, in particular, has placed higher demands on the research and development of self-antimicrobial materials. Currently, antimicrobial modification of fabrics has become a research hotspot in the development of antimicrobial products, and nanomaterials with excellent antimicrobial activity have become the preferred materials for fabric antimicrobial modification.

[0003] In recent years, high-entropy alloys (HEAs) have attracted considerable attention from researchers due to their outstanding structural stability, hydrogen evolution reaction activity, and antibacterial properties, and have become a rapidly growing research field. High-entropy alloy nanoparticles are novel nanoparticles containing five or more elements uniformly mixed into a solid solution structure. In addition to exhibiting the excellent structural stability, oxidation resistance, and corrosion resistance of HEAs, HEA nanoparticles exhibit unique physical properties in electrical, magnetic, optical, and thermal aspects due to their inherent nano-effects. Regarding antibacterial properties, copper or silver can be incorporated into HEA nanoparticles through a high-temperature reaction combined with quenching. The resulting multi-element nanoparticles possess both antibacterial elements and photothermal conversion properties, making them a promising nano-antibacterial agent.

[0004] Therefore, the development of antibacterial textiles by loading these novel functional nanoparticles with photothermal heating properties onto the surface of fabrics in a certain way to create a fabric that combines antibacterial elements with non-contact heating effects is of great significance. However, due to the unique properties of high-entropy alloy nanoparticles, such as high entropy, lattice distortion effects, and hysteretic diffusion, it is currently difficult to stably fix or load them onto the surface of fabrics or fibers through traditional methods. Summary of the Invention

[0005] Purpose of the invention: In view of the above problems, the present application provides a method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles. By taking advantage of the relatively negative "mixing enthalpy" of liquid metal and the adhesive effect of polymer, the two act as "binders" between liquid metal and other atoms, thereby stably fixing high-entropy alloy nanoparticles with antibacterial function on the surface of the fabric or fiber, significantly improving its antibacterial performance.

[0006] Technical solution: This application provides a method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles, comprising the following steps:

[0007] Step 1) washing, removing impurities and plasma treating the fabric material in sequence;

[0008] Step 2) mixing the liquid metal solution with the polymer solution to prepare a liquid metal / polymer mixed solution;

[0009] Step 3) coating the liquid metal / polymer mixed solution on the pretreated fabric surface to form a liquid metal-polymer mixed layer;

[0010] Step 4) dispersing high entropy alloy nanoparticles in a liquid medium, ultrasonically dispersing the dispersion, spraying the dispersion onto the fabric of step 3), and applying pressure at low temperature to obtain the final product.

[0011] Furthermore, the fabric material in step 1) is one of textile fabrics, non-woven fabrics, electrospun fiber felts, and single fibers, and the materials include but are not limited to one or more of cotton, wool, silk, linen, nylon, polyester, polypropylene, silk fibroin, polyvinylidene fluoride, polylactic acid, polycaprolactone, polylactic acid-glycolic acid, polyurethane, polystyrene, polyvinyl alcohol, polyethersulfone, polyacrylonitrile, and polyvinyl pyrrolidone.

[0012] Furthermore, in step 2), the liquid metal solution is composed of a dispersant, a solvent and liquid metal, and the ratio of the dispersant, the solvent and the liquid metal is 0.01-0.5:1-2:1, wherein the liquid metal is a gallium-based liquid alloy.

[0013] Furthermore, the polymer solution in step 2) is one or more of polyacrylamide, polyvinyl alcohol, polyethylene oxide, acrylic acid water-soluble glue, aqueous polyvinylidene fluoride, polyvinyl pyrrolidone, cyanoacrylate, polyethylene glycol, polyurethane, fibrin glue, silk fibroin, gelatin, albumin, chitosan, alginate, agarose, dextran and hyaluronic acid.

[0014] Furthermore, the viscosity of the polymer mixed solution prepared in step 2) is between 1-10 Pa·s; the liquid metal solution and the polymer solution are mixed at a mass ratio of 1:20-20:1 at 20-35° C., and ultrasonically dispersed.

[0015] Furthermore, in step 3), the coating temperature is 10-60° C. and the coating time is 1-120 min.

[0016] Furthermore, the high entropy alloy nanoparticles in step 4) are high entropy alloy nanoparticles composed of at least five elements, and contain one or two of copper and silver elements.

[0017] Furthermore, the high entropy alloy nanoparticles are dispersed in a liquid medium, and the concentration of the dispersion is 0.1-3.0 wt.%; the spraying time is 1-60 min; the low-temperature pressurization temperature is -10-20° C., the pressure is 1-20 MPa, and the time is 1-60 min.

[0018] Beneficial effects:

[0019] This method uses a liquid metal / polymer mixed solution as a "binder" between the high-entropy alloy nanoparticles and, under mild conditions, synergistically fixes the high-entropy alloy nanoparticles containing antimicrobial elements to the surface of the substrate. This provides excellent fastness to the high-entropy alloy nanoparticles, and leverages the antimicrobial elements and photothermal effects of the high-entropy alloy nanoparticles to impart excellent antimicrobial properties to the fabric (or fiber). This method is simple to prepare and readily adaptable to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a flow chart for preparing the fabric with surface-loaded high-entropy alloy nanoparticles in the present invention. DETAILED DESCRIPTION

[0021] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0022] Example 1:

[0023] A 10×10 cm silk fabric was first washed, cleaned, and plasma treated (with O2, 90 W power, and a treatment time of 30 seconds). Liquid gallium-indium alloy and dispersant were added to a solvent in sequence, stirred, and ultrasonically dispersed. The ratio of dispersant, solvent, and liquid gallium-indium alloy was 0.05:1:1. A polyacrylamide solution with a viscosity of 1.0 Pa·s was prepared. At 20°C, the two solutions were blended in a mass ratio of 1:20 between the liquid gallium-indium alloy and the polyacrylamide. At 25°C, the mixed solution was sprayed onto the pretreated silk fabric using a spray gun for 10 minutes. FeNiTiCrMnCu1 high-entropy alloy nanoparticles (with a Cu content of 1%) were ultrasonically dispersed in ethanol, with a dispersion concentration of 0.5 wt.%. The FeNiTiCrMnCu1 high entropy alloy nanoparticle dispersion was sprayed onto the silk fabric with a liquid metal-polymer mixed layer by a spraying method for 5 minutes; then the fabric was pressurized with 5 MPa at -5°C for 2 minutes.

[0024] Example 2:

[0025] The basic steps are the same as those in Example 1, except that: the coating object is polyester (PET) fabric; the ratio of the dispersant, the solvent and the liquid gallium-indium alloy is 0.1:1.2:1; a polyvinyl alcohol / silk fibroin mixed solution with a viscosity of 4.5 Pa·s is prepared; at 25°C, the two solutions are blended according to a mass ratio of the liquid gallium-indium alloy to the polyvinyl alcohol / silk fibroin of 1:10; at 30°C, the mixed solution is sprayed onto the pretreated PET fabric using a spray gun for 20 minutes; FeNiTiCrMnCu3 high entropy alloy nanoparticles (with a Cu element content of 3%) are ultrasonically dispersed in ethanol, and the dispersion concentration is 1.3wt.%; the spraying time is 8 minutes; and the fabric is pressurized to 8 MPa at 0°C for 5 minutes.

[0026] Example 3:

[0027] The basic steps are the same as those in Example 1, except that: the coating object is a polycaprolactone electrospun fiber membrane; the ratio of the dispersant, the solvent and the liquid gallium-indium alloy is 0.2:1.5:1; an acrylic acid / polyvinyl pyrrolidone mixed solution with a viscosity of 8.5 Pa·s is prepared; at 29°C, the two solutions are blended according to a mass ratio of the liquid gallium-indium alloy to the acrylic acid / polyvinyl pyrrolidone of 1:5; at 35°C, the above mixed solution is sprayed onto the pretreated polycaprolactone electrospun fiber membrane using a spray gun, and the spraying time is 30 minutes; CrMnCoFeCu4 high entropy alloy nanoparticles (wherein the Cu element content is 4%) are ultrasonically dispersed in ethanol, and the dispersion concentration is 2.0 wt.% at this time; the spraying time is 12 minutes; the fabric is pressurized at 12 MPa at 5°C for 10 minutes.

[0028] Example 4:

[0029] The basic steps are the same as those in Example 1, except that: the coating object is a polylactic acid non-woven fabric; the ratio of the dispersant, the solvent, and the liquid gallium-indium alloy is 0.3:1.6:1; a polycyanoacrylate / gelatin / chitosan mixed solution with a viscosity of 9.2 Pa·s is prepared; the two solutions are blended at a mass ratio of 1:1 between the liquid gallium-indium alloy and the polycyanoacrylate / gelatin / chitosan at 32°C; the mixed solution is sprayed onto the pretreated polylactic acid non-woven fabric using a spray gun at 40°C for 40 minutes; TiZrNbCrCu2Ag 2.5 High entropy alloy nanoparticles (Cu content of 2%, Ag content of 2.5%) were ultrasonically dispersed in ethanol, and the dispersion concentration was 2.3 wt.%; the spraying time was 16 min; and the fabric was pressurized at 15 MPa at 10° C. for 12 min.

[0030] Example 5:

[0031] The basic steps are the same as those in Example 1, except that: the coating object is polyester single fiber; the ratio of dispersant, solvent and liquid gallium-indium alloy is 0.4:1.8:1; a polyvinylidene fluoride / sodium alginate mixed solution with a viscosity of 10 Pa·s is prepared; the two solutions are blended at a mass ratio of liquid gallium-indium alloy to polyvinylidene fluoride / sodium alginate of 20:1 at 35°C; the mixed solution is sprayed onto the pretreated polyester single fiber using a spray gun at 50°C for 50 minutes; TiZrNbCrCu 2.5 Ag 2.5 High entropy alloy nanoparticles (containing 2.5% Cu and 2.5% Ag, respectively) were ultrasonically dispersed in ethanol at a dispersion concentration of 3.0 wt.%; the spraying time was 40 min; and the fiber was pressurized at 18 MPa at 14° C. for 15 min.

[0032] Example 6:

[0033] The basic steps are the same as those in Example 1, except that a polyacrylamide solution with a viscosity of 2.5 Pa·s is prepared.

[0034] Example 7:

[0035] The basic steps are the same as those in Example 1, except that a polyacrylamide solution with a viscosity of 4.0 Pa·s is prepared.

[0036] Example 8:

[0037] The basic steps are the same as those in Example 1, except that the mass ratio of the liquid gallium-indium alloy to the polyacrylamide is 1:10.

[0038] Example 9:

[0039] The basic steps are the same as those in Example 1, except that the mass ratio of the liquid gallium-indium alloy to the polyacrylamide is 1:5.

[0040] Embodiment 10:

[0041] The basic steps are the same as those in Example 1, except that the spraying time of the high entropy alloy nanoparticle dispersion is 10 min.

[0042] Example 11:

[0043] The basic steps are the same as those in Example 1, except that the spraying time of the high entropy alloy nanoparticle dispersion is 30 min.

[0044] Example 12:

[0045] The basic steps are the same as those in Example 1, except that the high entropy alloy nanoparticles selected are FeNiTiCrMnAg1.

[0046] Comparative Example 1: The basic steps are the same as those of Example 1, except that the liquid gallium-indium alloy / polyacrylamide mixed solution is not coated and the FeNiTiCrMnCu1 high entropy alloy nanoparticle dispersion is not sprayed.

[0047] Comparative Example 2: The basic steps are the same as those in Example 1, except that the dispersion of FeNiTiCrMnCu1 high-entropy alloy nanoparticles is not sprayed.

[0048] Comparative Example 3: The basic steps are the same as those in Example 1, except that the liquid gallium-indium alloy / polyacrylamide mixed solution is not coated.

[0049] Comparative Example 4: The basic steps are the same as those in Example 1, except that the high-entropy alloy nanoparticles selected are FeNiTiCrMn particles that do not contain Cu element.

[0050] Comparative Example 5: The basic steps are the same as those of Example 4, except that the high-entropy alloy nanoparticles selected are TiZrNbCrMn particles that do not contain Cu and Ag elements.

[0051] Comparative Example 6: The basic steps are the same as those in Example 12, except that the high-entropy alloy nanoparticles used are FeNiTiCrMn particles that do not contain the Ag element.

[0052] The samples of Examples 1, 6-9 and Comparative Example 3 were washed in a washing machine. After three washes, the mass loss rate of the high entropy alloy nanoparticles on the samples was tested. The results are shown in Table 1.

[0053] The samples of Examples 2-5 and 12 were washed in a washing machine. After three washes, the mass loss rate of the high entropy alloy nanoparticles on the samples was tested. The results are shown in Table 2.

[0054] The antibacterial rates of the samples of Examples 1-12 and Comparative Examples 1-6 were tested under no light and simulated sunlight conditions, and the results are shown in Table 3.

[0055] Table 1. Mass loss rate of high entropy alloy nanoparticles after washing three times in washing machine of samples of Examples 1, 6-9 and Comparative Example 3 of the present invention

[0056]

[0057] Table 2. Mass loss rate of high entropy alloy nanoparticles after washing three times in washing machine of samples 2-5 and 12 of the present invention

[0058]

[0059] Table 3. Antibacterial rate test results of samples of Examples 1-12 and Comparative Examples 1-6 in the present invention

[0060]

[0061]

[0062] By testing the mass loss rate of the high-entropy alloy nanoparticles on the fabric after three washes, the stability (reliability) of the high-entropy alloy nanoparticles on the fabric can be directly demonstrated. That is, the greater the particle mass loss rate, the worse its stability on the fabric. As shown in Table 1, the method of the present invention can improve the stability of high-entropy alloy nanoparticles on the fabric. Specifically, increasing the viscosity of the polymer solution and the mass ratio of the liquid gallium-indium alloy to the polymer within a certain range can help improve the stability of the high-entropy alloy nanoparticles on the fabric, indicating that the high-entropy alloy nanoparticles fixed by this method have strong reliability on the fabric.

[0063] In addition, as shown in Table 2, for different coating objects and loadings of different types and contents of high-entropy alloy nanoparticles, by regulating the composition of the liquid gallium-indium alloy solution, the viscosity of the polymer solution, the mass ratio of the liquid gallium-indium alloy to the polymer, and low-temperature pressurization and other process conditions, the high-entropy alloy nanoparticles can be made to have good stability on the fabric.

[0064] Table 3 shows that fabrics stably loaded with high-entropy alloy nanoparticles (containing one or both of copper and silver) exhibited excellent antibacterial properties in the absence of light. Specifically, greater surface stability of the high-entropy alloy nanoparticles (by manipulating the composition of the liquid gallium-indium alloy solution, the viscosity of the polymer solution, the mass ratio of the liquid gallium-indium alloy to the polymer, and the low-temperature pressurization conditions), higher loading (by manipulating the concentration of the high-entropy alloy nanoparticle dispersion and the spraying time of the high-entropy alloy nanoparticle dispersion), and changes in the type of high-entropy alloy nanoparticles (containing one or both of copper and silver) all enhanced the antibacterial properties of the fabrics. Furthermore, compared to the absence of light, the antibacterial rate of the fabrics was further improved after 30 minutes of simulated sunlight exposure. This improvement was observed even when the loaded high-entropy alloy nanoparticles did not contain copper or silver, indicating that the photothermal effect of high-entropy alloy nanoparticles can enhance the antibacterial rate of the fabrics.

[0065] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles, characterized in that: The steps include: Step 1) washing, removing impurities and plasma treating the fabric material in sequence; Step 2) mixing the liquid metal solution with the polymer solution to prepare a liquid metal / polymer mixed solution; the liquid metal solution comprises a dispersant, a solvent, and a liquid metal, wherein the ratio of the dispersant, the solvent, and the liquid metal is 0.01-0.5:1-2:1, wherein the liquid metal is a gallium-based liquid alloy; and the polymer solution is one or more of polyacrylamide, polyvinyl alcohol, polyethylene oxide, acrylic acid water-soluble glue, aqueous polyvinylidene fluoride, polyvinyl pyrrolidone, cyanoacrylate, polyethylene glycol, polyurethane, fibrin glue, silk fibroin, gelatin, chitosan, alginate, agarose, dextran, and hyaluronic acid; Step 3) coating the liquid metal / polymer mixed solution on the pretreated fabric surface to form a liquid metal-polymer mixed layer; Step 4) dispersing the high entropy alloy nanoparticles in a liquid medium, and after ultrasonic dispersion, spraying the dispersion onto the fabric in step 3), and applying pressure at low temperature to obtain the final product.

2. The method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles according to claim 1, wherein: The fabric material in step 1) is one of textile fabrics, non-woven fabrics, and electrospun fiber felt, and the material is not limited to one or more of cotton, wool, silk, linen, nylon, polyester, polypropylene, silk fibroin, polyvinylidene fluoride, polylactic acid, polycaprolactone, polylactic acid-glycolic acid, polyurethane, polystyrene, polyvinyl alcohol, polyethersulfone, polyacrylonitrile, and polyvinyl pyrrolidone.

3. The method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles according to claim 1, wherein: The viscosity of the polymer mixed solution prepared in step 2) is between 1-10 Pa·s; At 20-35° C., the liquid metal solution and the polymer solution are mixed in a mass ratio of 1:20-20:1, and ultrasonically dispersed.

4. The method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles according to claim 1, wherein: In step 3), the coating temperature is 10-60° C. and the coating time is 1-120 min.

5. The method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles according to claim 1, characterized in that: The high entropy alloy nanoparticles in step 4) are high entropy alloy nanoparticles composed of at least five elements, and contain one or two of copper and silver elements.

6. The method for preparing a fabric with surface-loaded high-entropy alloy nanoparticles according to any one of claims 1 to 5, characterized in that: The high entropy alloy nanoparticles are dispersed in a liquid medium, the concentration of the dispersion is 0.1-3.0 wt.%, the spraying time is 1-60 min, and the low-temperature pressurization temperature is -10-20°C, the pressure is 1-20 MPa, and the time is 1-60 min.

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