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CN-121135148-B - Antibacterial and antifouling ceramic material and preparation method thereof

CN121135148BCN 121135148 BCN121135148 BCN 121135148BCN-121135148-B

Abstract

The invention relates to the technical field of materials, and discloses an antibacterial and antifouling ceramic material and a preparation method thereof, wherein the ceramic material is prepared by taking potassium feldspar, sodium feldspar, functional modified halloysite and the like as raw materials through ball milling and mixing, the functional modified halloysite is a nano zinc oxide-loaded halloysite nanotube with a silica sol coated on the surface, the silica sol has extremely low surface energy, and a glaze layer formed by sintering ceramic glaze can be made to show hydrophobicity, so that the glaze layer is endowed with excellent antifouling self-cleaning performance. In addition, after the silica sol is coated, silver loaded in the halloysite nanotube is protected by the tube wall in the sintering process of the ceramic, and can be continuously released after a glaze layer is formed subsequently, so that the glaze layer is endowed with a long-acting slow-release antibacterial effect, and the nano zinc oxide has excellent photocatalytic antibacterial performance, can be cooperated with the silver, and can be added in a small amount, so that the antibacterial performance of the ceramic glaze can be greatly enhanced.

Inventors

  • QIU TAOHUI
  • QIU YANJIA
  • Qiu Haodian

Assignees

  • 潮州市创潮流陶瓷有限公司

Dates

Publication Date
20260512
Application Date
20250916

Claims (9)

  1. 1. The antibacterial and antifouling ceramic material is characterized by comprising the following raw materials in parts by weight: 30-45 parts of potassium feldspar, 20-30 parts of albite, 5-15 parts of kaolin, 3-5 parts of sepiolite, 2-4 parts of tourmaline, 1-2 parts of zirconia, 5-10 parts of zirconite, 10-15 parts of calcium carbonate, 2-6 parts of limestone, 1-2 parts of bauxite, 0.5-1.5 parts of functional modified halloysite, 1-2 parts of sodium carboxymethylcellulose and 1.5-3 parts of sodium tripolyphosphate; the preparation method of the functional modified halloysite comprises the following steps: Adding the loaded halloysite nanotube into deionized water, stirring and dispersing uniformly to form a dispersion liquid A, adding nano zinc oxide into the deionized water, performing ultrasonic dispersion uniformly to form a dispersion liquid B, adding N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine into absolute ethyl alcohol, stirring and mixing uniformly to prepare a mixed liquid; Mixing the dispersion liquid A and the dispersion liquid B to form a precursor liquid, adding the mixed liquid into the precursor liquid, adjusting the pH to 4-5 after adding, then raising the temperature to 60-70 ℃, keeping the temperature and stirring for 2-4 hours, adding silica sol, raising the temperature to 80-90 ℃ after adding, keeping the temperature and stirring for 4-8 hours, stopping heating, cooling and discharging, and collecting a product to obtain the functional modified halloysite; the supported halloysite nanotube is a silver-supported halloysite nanotube.
  2. 2. The antibacterial and antifouling ceramic material according to claim 1, wherein in the first step, the preparation method of the supported halloysite nanotubes comprises the following steps: s1, adding halloysite nanotubes into N, N-dimethylformamide, continuously adding an anhydride modifier and p-toluenesulfonic acid after uniform dispersion, and continuously stirring for 4-6 hours at the temperature of 90-100 ℃ after the addition, so as to obtain modified halloysite nanotubes; S2, dispersing the modified halloysite nanotubes in deionized water, then continuously adding a silver nitrate solution with the concentration of 0.1-0.2mol/L, controlling the ultrasonic frequency to be 80-100kHz after the addition, and separating out solid materials after ultrasonic treatment for 2-3 hours to form an intermediate material; and step S3, mixing the silver ammonia solution and the ascorbic acid solution, uniformly stirring, adding an intermediate material, controlling the ultrasonic frequency to be 100-120kHz after finishing adding, separating out a solid material after ultrasonic treatment for 1-2 hours, and obtaining the loaded halloysite nanotube through washing and vacuum drying treatment.
  3. 3. The antibacterial and antifouling ceramic material according to claim 2, wherein in step S1, the acid anhydride modifier is any one of succinic anhydride, maleic anhydride or glutaric anhydride.
  4. 4. The antibacterial and antifouling ceramic material according to claim 2, wherein in step S3, the concentration of the silver-ammonia solution is 0.2-0.3mol/L, and the concentration of the ascorbic acid solution is 0.1-0.2mol/L.
  5. 5. An antimicrobial and antifouling ceramic material according to claim 1, wherein in step one, the mass fraction of the dispersion a is 10-20%.
  6. 6. An antimicrobial and antifouling ceramic material according to claim 1, wherein in step one, the mass fraction of the dispersion B is 5-10%.
  7. 7. The antibacterial and antifouling ceramic material according to claim 1, wherein in the first step, the mass fraction of the mixed solution is 1-2%.
  8. 8. The antibacterial and antifouling ceramic material according to claim 1, wherein in the second step, the volume ratio of the precursor solution to the mixed solution is 3-5:1.
  9. 9. A method for preparing the antibacterial and antifouling ceramic material according to claim 1, comprising the steps of: Firstly, weighing and preparing all raw materials according to parts by weight; Secondly, adding potassium feldspar, albite, kaolin, sepiolite, tourmaline, zirconia, zirconite, calcium carbonate, limestone, bauxite and functional modified halloysite into a mixer, mechanically stirring and uniformly mixing, transferring into a ball mill, and ball milling until the screen residue of a ten-thousand-hole sieve is lower than 0.05%, thereby forming a base material; Thirdly, adding sodium carboxymethylcellulose and sodium tripolyphosphate into the base material, stirring uniformly, continuing to add, regulating the specific gravity to 1.5-1.65g/cm 3 , standing and defoaming to obtain the ceramic material.

Description

Antibacterial and antifouling ceramic material and preparation method thereof Technical Field The invention relates to the technical field of materials, in particular to an antibacterial and antifouling ceramic material and a preparation method thereof. Background Ceramics are important carriers of human civilization, and their development history extends through various stages of human society. The traditional ceramic is prepared by taking clay as a main raw material through processes such as molding, calcining and the like, and modern ceramic materials are expanded to advanced ceramic systems such as oxides, nitrides, carbides and the like, and are widely applied to the fields of bathroom, household porcelain, electronics, aerospace, medical treatment and the like. Whether conventional or advanced, glazes are core materials that enhance their performance and function. The glaze is a vitreous thin layer covered on the surface of the ceramic body, and is prepared by mixing mineral raw materials such as quartz, feldspar, clay and the like with chemical raw materials in proportion to prepare glaze slurry, and combining the glaze slurry with the body after high-temperature sintering. The ceramic glaze has the core functions of optimizing surface performance, improving mechanical strength, decorating, protecting and the like, however, along with the continuous development of ceramics in the daily porcelain field, the functionality of the ceramic glaze is gradually paid attention to, in particular to the antibacterial and antifouling directions, and as products such as ceramic cups, ceramic basins, ceramic bathrooms and the like are in high humidity and high pollution environments for a long time, the surfaces of the products are easy to become warm beds for microorganism breeding, stains are accumulated, peculiar smell is generated and even diseases are spread, so that the development of the ceramic glaze with the antibacterial and antifouling functions has important significance. At present, heavy metals such as silver are adopted as an antibacterial additive of ceramic glaze, however, during the high-temperature sintering process of ceramic, silver can be separated out and ablated, so that the effect of the silver is greatly reduced. Disclosure of Invention In order to solve the problems mentioned in the background art, the invention aims to provide an antibacterial and antifouling ceramic material and a preparation method thereof. The aim of the invention can be achieved by the following technical scheme: an antibacterial and antifouling ceramic material comprises the following raw materials in parts by weight: 30-45 parts of potassium feldspar, 20-30 parts of albite, 5-15 parts of kaolin, 3-5 parts of sepiolite, 2-4 parts of tourmaline, 1-2 parts of zirconia, 5-10 parts of zirconite, 10-15 parts of calcium carbonate, 2-6 parts of limestone, 1-2 parts of bauxite, 0.5-1.5 parts of functional modified halloysite, 1-2 parts of sodium carboxymethyl cellulose and 1.5-3 parts of sodium tripolyphosphate. As a further scheme of the invention, the preparation method of the functional modified halloysite comprises the following steps: Adding the loaded halloysite nanotube into deionized water, stirring and dispersing uniformly to form a dispersion liquid A, adding nano zinc oxide into the deionized water, performing ultrasonic dispersion uniformly to form a dispersion liquid B, adding N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine into absolute ethyl alcohol, stirring and mixing uniformly to prepare a mixed liquid; Mixing the dispersion liquid A and the dispersion liquid B to form a precursor liquid, adding the mixed liquid into the precursor liquid, adjusting the pH to 4-5 after adding, then raising the temperature to 60-70 ℃, preserving heat and stirring for 2-4 hours, adding silica sol, raising the temperature to 80-90 ℃ after adding, stopping heating after preserving heat and stirring for 4-8 hours, cooling and discharging, and collecting the product to obtain the functional modified halloysite. In a first step, the preparation method of the loaded halloysite nanotube comprises the following steps: s1, adding halloysite nanotubes into N, N-dimethylformamide, continuously adding an anhydride modifier and p-toluenesulfonic acid after uniform dispersion, and continuously stirring for 4-6 hours at the temperature of 90-100 ℃ after the addition, so as to obtain modified halloysite nanotubes; S2, dispersing the modified halloysite nanotubes in deionized water, then continuously adding a silver nitrate solution with the concentration of 0.1-0.2mol/L, controlling the ultrasonic frequency to be 80-100kHz after the addition, and separating out solid materials after ultrasonic treatment for 2-3 hours to form an intermediate material; and step S3, mixing the silver ammonia solution and the ascorbic acid solution, uniformly stirring, adding an intermediate material, controlling the ultrasonic f