CN115530181B

CN115530181B - High-temperature-resistant nano antibacterial agent, preparation method thereof and antibacterial ceramic product containing same

Info

Publication number: CN115530181B
Application number: CN202211192355.6A
Authority: CN
Inventors: 郑文富; 李小兰; 赵宇亮
Original assignee: GBA National Institute for Nanotechnology Innovation
Current assignee: GBA National Institute for Nanotechnology Innovation
Priority date: 2022-09-28
Filing date: 2022-09-28
Publication date: 2023-07-11
Anticipated expiration: 2042-09-28
Also published as: CN115530181A

Abstract

The invention relates to a high-temperature-resistant nano antibacterial agent, a preparation method thereof and an antibacterial ceramic product containing the same. The preparation method comprises the following steps: mixing natural ore powder and water to prepare a mixture A; mixing the mixture A with a dispersing agent to prepare a mixture B; mixing the mixture B with grinding balls, and ball milling to prepare the high-temperature-resistant nano antibacterial agent. The invention uses natural ore powder as raw materials, mixes the raw materials with water, and adds a dispersing agent for ball milling, thus preparing the high-temperature resistant antibacterial agent, which has the advantages of low cost, simple preparation steps, uniform particle size and controllable particle size, and particularly, the obtained antibacterial agent can withstand the high temperature required by firing porcelain, can be directly mixed with glaze material for firing after being coated on the surface of a green body in the process of preparing the antibacterial product by taking the antibacterial agent as an antibacterial component, simplifies the preparation process of the antibacterial product, and can obtain better antibacterial performance even if the antibacterial product is subjected to the firing high temperature of about 1200 ℃.

Description

High-temperature-resistant nano antibacterial agent, preparation method thereof and antibacterial ceramic product containing same

Technical Field

The invention belongs to the technical field of porcelain preparation, and particularly relates to a high-temperature-resistant nano antibacterial agent, a preparation method thereof and an antibacterial ceramic product containing the same.

Background

In recent years, ceramics are closely related to our lives as an indispensable material for the construction industry. Microorganisms such as bacteria are particularly easy to breed in places such as toilets, kitchens and bathrooms in living environments due to high humidity, and ceramic products in the environments need to have certain antibacterial property in order to make the living environments of the living environments healthier and safer.

Conventional ceramic articles with antimicrobial properties, such as: an antibacterial ceramic product described in CN101360696a, which has metallic nanoparticles having an average particle diameter of at least silver of 200nm or less on the surface, however, the use of silver ions as an antibacterial component is costly, is not conducive to mass production, and affects color; the glaze of the ceramic article described in CN 113061055A has an adhesive layer and an antimicrobial coating; the adhesive layer is positioned between the ceramic and the antibacterial coating; the preparation raw materials of the antibacterial coating comprise antibacterial nano powder materials, wherein the antibacterial nano powder materials are nano powder materials with antibacterial properties and the one-dimensional length of 1-100 nanometers, the preparation raw materials of the adhesive are mineral mud or mineral small film stained paper, and complicated steps are needed for preparing the ceramic product to ensure that the antibacterial effect is finally obtained.

In view of this, the present invention has been made.

Disclosure of Invention

Based on the above, the invention aims to provide a preparation method of a high-temperature-resistant nano antibacterial agent, and the high-temperature-resistant nano antibacterial agent obtained by the preparation method can be directly mixed with glaze for high-temperature firing in the process of being used for ceramic products, and is convenient and low in cost.

In a first aspect of the present invention, there is provided a method for preparing a high temperature resistant nano-antibacterial agent, the method comprising the steps of:

mixing natural ore powder and water to prepare a mixture A;

mixing the mixture A with a dispersing agent to prepare a mixture B;

mixing the mixture B with grinding balls, and ball milling to prepare a high-temperature-resistant nano antibacterial agent;

the grinding ball is a zirconia ball, and the preparation method has the following technical characteristics:

(1) The mass ratio of the natural ore powder to the water is 1: (100-200);

(2) The mass ratio of the mixture A to the dispersing agent is 1: (0.5-2);

(3) The mass ratio of the mixture B to the zirconia balls is 1: (2-4);

(4) The grinding conditions include: the grinding speed is 300rpm-500rpm, and the grinding time is 2h-3h;

or alternatively, the process may be performed,

the grinding ball is an agate ball, and the preparation method has the following technical characteristics:

(1) The mass ratio of the natural ore powder to the water is 1: (75-150);

(2) The mass ratio of the mixture A to the dispersing agent is 1: (0.5-1.5);

(3) The mass ratio of the mixture B to the agate balls is 1: (2-6);

(4) The grinding conditions include: the grinding speed is 300rpm-500rpm, and the grinding time is 2h-3h.

In some embodiments of the invention, the natural ore fines are selected from one or more of quartz fines, talc fines, calamine fines, shell fines, limestone fines, and feldspar fines.

In some embodiments of the invention, the dispersing agent is selected from one or more of chitosan, methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, and polyvinyl alcohol.

In some embodiments of the present invention, the natural ore nanoparticles contained in the high temperature resistant nano-antimicrobial agent have an average particle size of 3nm to 35nm and a particle size range of 1nm to 50nm.

In some embodiments of the invention, the zirconia balls have a diameter of 0.1mm to 0.5mm.

In some embodiments of the invention, the agate balls have a diameter of 0.1cm to 2cm.

In a second aspect of the present invention, there is provided a high temperature resistant nano-antimicrobial agent prepared by the preparation method of the first aspect.

In a third aspect of the present invention, there is provided an antimicrobial ceramic article having a glaze layer comprising a glaze and the high temperature resistant nano antimicrobial agent of the second aspect.

In some embodiments of the invention, the mass ratio of the glaze to the high temperature resistant nano-antimicrobial agent is 1: (0.001-0.15).

In a fourth aspect of the present invention, there is provided a method for preparing the antibacterial ceramic product, the method comprising the steps of:

mixing the glaze with the high-temperature-resistant nano antibacterial agent to prepare an antibacterial glaze;

and (3) coating the antibacterial glaze on the surface of the blank to form an antibacterial glaze layer, and firing to prepare the antibacterial ceramic product.

In some embodiments of the invention, the firing conditions include: the temperature is 1200-1300 ℃ and the time is 2-6 h.

In some embodiments of the invention, the antimicrobial glaze layer has a thickness of 0.5cm to 0.9cm.

Compared with the prior art, the invention has the following beneficial effects:

the invention takes natural ore powder as raw material, mixes the natural ore powder with a proper amount of water, adds a dispersing agent for moderate ball milling, thus preparing the high temperature resistant antibacterial agent, the antibacterial mechanism is that the natural ore powder after ball milling has a smaller specific surface area, after high temperature firing, the surface can be seen to have a plurality of obvious small protrusions through electron microscopy, therefore, the antibacterial mechanism of the prepared high temperature resistant antibacterial agent has a great part of reasons of physical antibacterial, and the antibacterial intensity has a great relation with the average nanometer particle diameter of the natural ore powder obtained after ball milling. Therefore, the preparation cost for preparing the high-temperature-resistant antibacterial agent is low, the preparation steps are simple, the particle size is uniform, the particle size is controllable, and particularly, the obtained antibacterial agent can withstand the high temperature required by firing porcelain, can be directly mixed with glaze and then coated on the surface of a green body for firing in the process of preparing an antibacterial product by taking the antibacterial agent as an antibacterial component, simplifies the preparation process of the antibacterial product, and can obtain better antibacterial performance even if the antibacterial agent is subjected to the firing high temperature of about 1200 ℃. In addition, the addition of the high-temperature-resistant antibacterial agent has no obvious influence on the color performance of porcelain products. Meanwhile, the material adopted by the invention is natural ore, has extremely high safety and good stability, is environment-friendly and has no pollution.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application and to more fully understand the present application and its advantageous effects, the following brief description will be given with reference to the accompanying drawings, which are required to be used in the description of the embodiments. It is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive effort to a person skilled in the art.

FIG. 1 is a graph showing the particle size measurement of the high temperature resistant nano-antimicrobial agent obtained by ball milling in example 1, wherein the particle size is between 1nm and 50nm, and the average particle size is 34.88nm;

FIG. 2 is a graph showing the particle size measurement of the high temperature resistant nano-antimicrobial agent obtained by ball milling in example 2, wherein the particle size is 1nm-10nm, and the average particle size is 4.25nm;

FIG. 3 is a microscopic lower surface structure of the antibacterial ceramic prepared in example 1;

FIG. 4 is an antibacterial ceramic prepared in example 1.

Detailed Description

The present invention will be described in further detail with reference to the drawings, embodiments and examples. It should be understood that these embodiments and examples are provided solely for the purpose of illustrating the invention and are not intended to limit the scope of the invention in order that the present disclosure may be more thorough and complete. It will also be appreciated that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein, but may be modified or altered by those skilled in the art without departing from the spirit of the invention, and equivalents thereof fall within the scope of the present application. Furthermore, in the following description, numerous specific details are set forth in order to provide a more thorough understanding of the invention, it being understood that the invention may be practiced without one or more of these details.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing the embodiments and examples only and is not intended to be limiting of the invention.

Terminology

Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:

the term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from "and/or", "or/and", "and/or", it should be understood that, in this application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).

The terms "plurality", "plural", "multiple", and the like in the present invention refer to, unless otherwise specified, an index of 2 or more in number. For example, "one or more" means one kind or two or more kinds.

As used herein, "a combination thereof," "any combination thereof," and the like include all suitable combinations of any two or more of the listed items.

The "suitable" in the "suitable combination manner", "suitable manner", "any suitable manner" and the like herein refers to the fact that the technical scheme of the present invention can be implemented, the technical problem of the present invention is solved, and the technical effect expected by the present invention is achieved.

Herein, "preferred", "better", "preferred" are merely to describe better embodiments or examples, and it should be understood that they do not limit the scope of the invention.

In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.

In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.

In the present invention, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature being indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.

In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.

In the present invention, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. Where a numerical range merely refers to integers within the numerical range, including both end integers of the numerical range, and each integer between the two ends, unless otherwise indicated, each integer is recited herein as directly, such as where t is an integer selected from 1 to 10, and where t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.

The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.

In the present invention,% (w/w) and wt% each represent weight percent,% (v/v) represents volume percent, and% (w/v) represents mass volume percent.

All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Unless otherwise contradicted by purpose and/or technical solution of the present application, the cited documents related to the present invention are incorporated by reference in their entirety for all purposes. When reference is made to a cited document in the present invention, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the cited document are also incorporated. In the case of the cited documents, examples and preferred modes of the cited relevant technical features are incorporated into the present application by reference, but are not limited to the embodiments that can be implemented. It should be understood that when a reference is made to the description herein, it is intended to control or adapt the present application in light of the description herein.

The traditional preparation method of the nano-scale antibacterial deodorizing composite powder prepared from ore powder, for example, the preparation method disclosed in CN1390892A, has the defects of various raw material types, complex preparation steps, and obviously reduced antibacterial performance under the condition of directly mixing the nano-scale antibacterial deodorizing composite powder with glaze and firing at a high temperature of about 1200 ℃, and the antibacterial property of the obtained porcelain product is not in accordance with the requirements. Based on the above, the invention provides a preparation method of the high-temperature-resistant nano antibacterial agent with few raw materials and simple preparation steps.

First aspect of the invention

The invention provides a preparation method of a high-temperature-resistant nano antibacterial agent, which comprises the following steps:

mixing natural ore powder and water to prepare a mixture A;

mixing the mixture A with a dispersing agent to prepare a mixture B;

(1) The mass ratio of the natural ore powder to the water is 1: (100-200);

(2) The mass ratio of the mixture A to the dispersing agent is 1: (0.5-2);

(3) The mass ratio of the mixture B to the zirconia balls is 1: (2-4);

or alternatively, the process may be performed,

(1) The mass ratio of the natural ore powder to the water is 1: (75-150);

(2) The mass ratio of the mixture A to the dispersing agent is 1: (0.5-1.5);

(3) The mass ratio of the mixture B to the agate balls is 1: (2-6);

In one example, the natural ore powder is selected from one or more of quartz powder, talcum powder, calamine powder, shell powder, limestone powder and feldspar powder.

In one example, the mass ratio of the natural ore fines to the water is 1: (1-1000), for example 1:1, 1:5, 1:10, 1:50, 1:100, 1:75, 1:500, 1:750, 1:1000.

In one example, the dispersant is selected from one or more of chitosan, methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, and polyvinyl alcohol.

In one example, the mass ratio of the mixture a to the dispersant is 1: (0.1-50), for example 1:0.1, 1:0.5, 1:1. 1:5. 1: 10. 1: 15. 1: 20. 1: 25. 1: 30. 1: 35. 1: 40. 1: 45. 1:50.

in one example, the average particle size of the natural ore nanoparticles contained in the high temperature resistant nano-antimicrobial agent is 3nm to 35nm, and the particle size range is 1nm to 50nm.

In one example, the zirconia balls have a diameter of 0.1mm to 0.5mm.

In one example, the grinding balls are zirconia balls, and the mass ratio of the natural ore powder to the water is, for example, 1: 100. 1: 110. 1: 120. 1: 130. 1: 140. 1: 150. 1: 160. 1: 170. 1: 180. 1: 190. 1:200, the mass ratio of the mixture A to the dispersant is, for example, 1:0.5, 1:0.8, 1:1.2, 1:1.5, 1:1.8, 1:2, the mass ratio of the mixture B to the zirconia balls is, for example, 1:2. 1:2.2, 1:2.5, 1:2.8, 1:3. 1:3.2, 1:3.5, 1:3.7, 1:4, the polishing rate is, for example, 300rpm, 325rpm, 350rpm, 400rpm, 425rpm, 450rpm, 475rpm, 500rpm. The polishing time is, for example, 2 hours, 2.5 hours, or 3 hours.

In one example, the agate balls have a diameter of 0.1cm to 2cm.

In one example, the grinding balls are agate balls, and the mass ratio of the natural ore powder to the water is, for example, 1:75, 1: 80. 1: 85. 1: 90. 1: 95. 1:100, 1:125, 1: 140. 1:150, the mass ratio of the mixture A to the dispersant is, for example, 1:0.5, 1:1. 1:1.5, the mass ratio of the mixture B to the agate balls is, for example: 1:2. 1:1.25, 1:1.5, 1:2. 1:2.5, 1:3. 1:3.5, 1:4. 1:4.5, 1:5. 1:5.5, 1: the polishing rate was, for example, 300rpm, 325rpm, 350rpm, 400rpm, 425rpm, 450rpm, 475rpm, and 500rpm, and the polishing time was, for example, 2 hours, 2.5 hours, and 3 hours.

Second aspect of the invention

The invention provides a high-temperature-resistant nano antibacterial agent, which is prepared by the preparation method in the first aspect.

Third aspect of the invention

The invention provides an antibacterial ceramic product, which comprises glaze and the high-temperature-resistant nano antibacterial agent in the second aspect of the invention.

In one example, the mass ratio of the glaze to the high temperature resistant nano-antimicrobial agent is 1: (0.001-0.15), for example 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.15.

fourth aspect of the invention

The invention provides a preparation method of the antibacterial ceramic product in the third aspect, which comprises the following steps:

In one example, the firing conditions include: the temperature is 1200-1300 ℃ and the time is 2-6 h. The temperature is 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃,1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃ 1300 ℃ and the time is 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours and 4.5 hours, for example.

In one example, the thickness of the antimicrobial glaze layer is 0.5cm to 0.9cm. The thickness is, for example, 0.5cm, 0.55cm, 0.6cm, 0.65cm, 0.7cm, 0.75cm, 0.8cm, 0.85cm, 0.9cm.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples, in which specific conditions are not noted, are preferably referred to the guidelines given in the present invention, and may be according to the experimental manual or conventional conditions in the art, the conditions suggested by the manufacturer, or the experimental methods known in the art.

In the specific examples described below, the measurement parameters relating to the raw material components, unless otherwise specified, may have fine deviations within the accuracy of weighing. Temperature and time parameters are involved, allowing acceptable deviations from instrument testing accuracy or operational accuracy.

Example 1

The embodiment provides a preparation method of a high-temperature-resistant nano antibacterial agent and antibacterial ceramic, which comprises the following steps:

1. preparation of high-temperature-resistant nano antibacterial agent

S1: mixing natural ore quartz stone and talcum powder (mass ratio of 1:1), sieving, adding water, mixing, and mixing natural ore: the water is 1:100 (mass ratio) to obtain a mixture A.

S2: dispersing agent (chitosan and methyl cellulose with mass ratio of 1:2.5) is added into the mixture A, and the mixture A is: the dispersant is 1:0.5 (mass ratio) to obtain a mixture B.

S3: adding a certain proportion (0.1 mm-0.5 mm) of zirconia beads to the mixture B for ball milling, wherein the mixture B comprises the following components: zirconia beads were 1:2 (mass ratio), the ball milling time is 2 hours, the ball milling rotating speed is 420rpm, and the high-temperature resistant nano antibacterial agent with uniform size and particle size ranging from 1nm to 50nm is obtained, and is shown in figure 1.

In the step S3, the mechanical-chemical modification temperature of the ball mill is 20-40 ℃ in the experimental process, the experimental influence caused by climate change in four seasons is avoided, the conditions are simple, and the method is suitable for the normal pressure of the process amplification experiment.

2. Preparation of antibacterial ceramic

S4: adding the nano antibacterial agent obtained in the step S3 into glaze (the mass ratio of the nano antibacterial agent to the glaze is 0.002:1) according to a certain proportion, ball-milling for 30min, coating on the surface of ceramic, and firing for 2h in a 1250 ℃ furnace with the thickness of 0.5cm to obtain the ceramic with surface antibacterial property, wherein the ceramic is shown in figures 3 and 4.

Example 2

1. preparation of high-temperature-resistant nano antibacterial agent

S1: natural ore calamine, shell powder and limestone (mass ratio of 1:1:1) are sieved, water is added, and natural ore is added: the water is 1:200 (mass ratio) to obtain a mixture A.

S2: dispersing agent (sodium carboxymethylcellulose and polyvinyl alcohol in a mass ratio of 2:0.5) is added into the mixture A, and the mixture A is prepared by the following steps: the dispersant is 1:1.8 (mass ratio) to obtain a mixture B.

S3: adding a certain proportion (0.1 mm-0.5 mm) of zirconia beads to the mixture B for ball milling, wherein the mixture B comprises the following components: zirconia beads were 1:4 (mass ratio), the ball milling time is 3 hours, the ball milling rotating speed is 320rpm, and the high-temperature resistant nano antibacterial agent with uniform size and particle size in the range of 1-10nm is obtained, and is shown in figure 2.

2. Preparation of antibacterial ceramic

S4: adding the nano antibacterial agent obtained in the step S3 into glaze (the mass ratio of the nano antibacterial agent to the glaze is 0.005:1) according to a certain proportion, ball-milling for 30min, coating on the surface of ceramic, firing for 6h in a furnace with the thickness of 0.8cm and the temperature of 1200 ℃ to obtain the ceramic with surface antibacterial property.

Example 3

1. preparation of high-temperature-resistant nano antibacterial agent

S1: natural ore quartz stone, talcum powder and calamine (mass ratio of 1:1:1) are sieved, mixed with water, and natural ore is obtained: the water is 1:75 (mass ratio) to obtain a mixture A.

S2: to mixture a was added a dispersant (sodium carboxymethyl cellulose), mixture a: the dispersant is 1:0.8 (mass ratio) to obtain a mixture B.

S3: adding a certain proportion (0.1 cm-2 cm) of agate beads to the mixture B for ball milling, wherein the mixture B comprises the following components: agate beads were 1:2.5 The ball milling time is 2 hours, the ball milling rotating speed is 420rpm, and the high-temperature resistant nano antibacterial agent with uniform size and particle size range of 1-50nm is obtained.

2. Preparation of antibacterial ceramic

S4: adding the nano antibacterial agent obtained in the step S3 into glaze (the mass ratio of the nano antibacterial agent to the glaze is 0.02:1) according to a certain proportion, ball-milling for 30min, coating on the surface of ceramic, firing for 2h in a furnace with the thickness of 0.7cm and the temperature of 1200 ℃ to obtain the ceramic with surface antibacterial property.

Example 4

1. preparation of high-temperature-resistant nano antibacterial agent

S1: natural ore shell powder, limestone and feldspar (mass ratio of 1:1:1), sieving, adding water, mixing, and natural ore: the water is 1:125 (mass ratio) to obtain a mixture A.

S2: to mixture a was added a dispersant (polyvinyl alcohol), mixture a: the dispersant is 1:1.5 (mass ratio) to obtain a mixture B.

S3: adding a certain proportion (0.1 cm-2 cm) of agate beads to the mixture B for ball milling, wherein the mixture B comprises the following components: agate beads were 1:5.5 The ball milling time is 3h, the ball milling rotating speed is 350rpm, and the high-temperature resistant nano antibacterial agent with uniform size and particle size range of 1nm-50nm is obtained.

2. Preparation of antibacterial ceramic

S4: adding the nano antibacterial agent obtained in the step S3 into glaze (the mass ratio of the nano antibacterial agent to the glaze is 0.08:1) according to a certain proportion, ball-milling for 30min, coating on the surface of ceramic, firing for 6h in a furnace with the thickness of 0.9cm at 1300 ℃ to obtain the ceramic with surface antibacterial property.

Comparative example 1

This comparative example is a comparative example of example 1, and differences with respect to example 1 include:

s1: the mass ratio of the natural ore powder to the water is 1:1, a step of;

s2: the mass ratio of the mixture A to the dispersing agent is 1:0.1;

s3: the mass ratio of the mixture B to the zirconia balls is 1:0.1; the grinding conditions include: the polishing rate was 50rpm and the polishing time was 8 hours.

Comparative example 2

s1: the mass ratio of the natural ore powder to the water is 1:800;

s2: the mass ratio of the mixture A to the dispersing agent is 1:45;

s3: the mass ratio of the mixture B to the zirconia balls is 1:12; the grinding conditions include: the polishing rate was 800rpm and the polishing time was 0.1h.

Comparative example 3

This comparative example is a comparative example of example 3, and differences with respect to example 3 include:

s1: the mass ratio of the natural ore powder to the water is 1:75;

s2: the mass ratio of the mixture A to the dispersing agent is 1:0.8;

s3: the mass ratio of the mixture B to the agate balls is 1:0.1; the grinding conditions include: the grinding speed is 50rpm, the grinding time is 0.1h, and the additive with uniform size and particle size range of 1000-2000nm is obtained.

Comparative example 4

s1: the mass ratio of the natural ore powder to the water is 1:850;

s2: the mass ratio of the mixture A to the dispersing agent is 1:40, a step of performing a;

s3: the mass ratio of the mixture B to the agate balls is 1:30; the grinding conditions include: the polishing rate was 800rpm and the polishing time was 8 hours.

Comparative example 5

s1: the mass ratio of the natural ore powder to the water is 1:850;

s2: the mass ratio of the mixture A to the dispersing agent is 1:50;

s3: the mass ratio of the mixture B to the agate balls is 1:30; the grinding conditions include: the polishing rate was 900rpm and the polishing time was 8 hours.

Comparative example 6

s1: the mass ratio of the natural ore powder to the water is 1:900;

s2: the mass ratio of the mixture A to the dispersing agent is 1:45;

s3: the mass ratio of the mixture B to the agate balls is 1:35; the grinding conditions include: the polishing rate was 900rpm and the polishing time was 0.1h.

Comparative example 7

The comparative example provides a method for preparing ceramic, comprising the following steps:

adding water into the glaze, and adding sodium carboxymethyl cellulose, wherein the glaze comprises the following steps of: water: sodium carboxymethylcellulose is 100:560:0.7 Ball milling for 30min, coating on the surface of ceramic, firing for 4h at 1200 ℃ with the thickness of 0.8cm, and obtaining the ceramic.

Antibacterial property detection

In the process of preparing the antibacterial ceramic, the high-temperature resistant nano antibacterial agents prepared by the examples with different concentrations are dissolved in nutrient broth by adopting an agar dilution method, bacteria are inoculated, and the minimum concentration of the product for inhibiting the growth of the tested bacteria, namely the minimum inhibitory concentration (Minimal Inhibitory Concentration, MIC) is determined by observing the growth or not of the bacteria. The results showed that the high temperature resistant nano-antimicrobial agents of examples 1 to comparative example 6 were each effective in inhibiting staphylococcus aureus ATCC6538 and escherichia coli ATCC8739, and the MICs of staphylococcus aureus ATCC6538 and escherichia coli ATCC8739 were each lower than 100ppm.

Further, the antibacterial property of the obtained antibacterial ceramic was examined: at present, the antibacterial performance of the ceramic surface is evaluated by referring to a method specified in national recommended standard GB/T31402-2015 "test method for antibacterial performance of Plastic surface", and staphylococcus aureus and escherichia coli are used as indicator bacteria. If the sterilization rate is larger than or equal to 90%, the continuous antibacterial effect is judged in the period.

1. Test strain: staphylococcus aureus ATCC6538, escherichia coli ATCC8739.

2. The test steps are as follows:

(1) Autoclaving: 24 samples of 5 cm. Times.5 cm ceramics (as a sample group) having surface antibacterial properties and 12 ceramics fired in comparative example 1 (as a blank group) were prepared, placed in an autoclave, and sterilized at (121.+ -. 2) ℃for 15 minutes or more.

(2) The bacterial suspension was diluted with 1/500NB to a bacterial concentration of 2.5X10 ⁵ CFU/mL-10×10 ⁵ Between CFU/mL, used as inoculum, the bacterial count was determined using the counter plate method.

(3) Style inoculation: respectively placing 5cm×5cm plates in sterile culture dishes, sucking 0.4mL of inoculation liquid by a pipette, dripping onto the surface of each sample, covering a film with the thickness of 4cm×4cm on the inoculated bacteria liquid, slightly pressing the film to diffuse the bacteria liquid to the periphery so as to ensure that the bacteria liquid does not overflow from the edge of the film, and finally covering the culture dishes.

(4) Culturing: culturing (24+ -1) h at (35+ -1) deg.C with relative humidity of no less than 90%.

(5) The test sample group and the blank control group are placed in a 37 ℃ incubator, incubated for 48 hours, and the results are observed.

(6) And respectively recovering strains, and calculating recovery rate.

3. Results

As can be seen from Table 1, the antibacterial ceramic prepared in examples 1 to 4, which was added with the high temperature resistant antibacterial agent, had significantly higher antibacterial (anti) rates against E.coli and Staphylococcus aureus than the comparative example, and the high temperature resistant antibacterial agents prepared in examples 1 to 4 were subjected to high temperature firing, and still maintained excellent antibacterial effects. The antibacterial effect of the antibacterial ceramics prepared in comparative examples 1 to 6 was slightly improved with respect to comparative example 7, but the overall was weaker with respect to examples 1 to 4. In comparative example 1, no antibacterial agent is added, and the ceramic is fired only by the same process and condition as the common glaze, so that the antibacterial rate is not more than or equal to 90%. Therefore, to prepare ceramics with surface antibacterial property, an antibacterial agent with better high-temperature resistance needs to be added.

Table 1, examples and comparative examples for bacteriostasis

	Coli (bacteriostasis%)	Staphylococcus aureus (bacteriostasis rate%)
			Example 1	98.9％	99.9％
Example 2	99.9％	99.9％
			Example 3	99.9％	99.9％
Example 4	99.9％	99.9％
			Comparative example 1	32.4％	38.5％
Comparative example 2	35.4％	40.3％
			Comparative example 3	28.7％	35.4％
Comparative example 4	31.4％	34.6％
			ComparisonExample 5	28.6％	30.7％
Comparative example 6	29.8％	31.2％
			Comparative example 7	21.4％	25.1％

In summary, the invention ball-mills the natural ore to 1nm-50nm by ball-milling process, and adds the natural ore with specific nano particle size into glaze according to a certain proportion to fire the antibacterial porcelain product, compared with the prior art, the invention has the beneficial effects that: (1) raw material sources are wide: pure natural ore is adopted, the source is wide, and the specific ball milling process is used for preparing the nano antibacterial agent with specific nano particle size. (2) high biosafety: the raw materials are green and environment-friendly, do not involve any toxic reagent, and are easy to degrade. (3) The ceramic antibacterial agent is easy to provide for enterprises, has wide sources of raw materials, simple manufacturing process and controllable cost, and is suitable for mass production of antibacterial ceramics with surface antibacterial property by enterprises. (4) Only a little is needed to be added on the surface of the ceramic, so that the ceramic has good antibacterial property under the condition that the performances of the original ceramic are not affected, and the ceramic can be used for surface antibacterial and mildew-proof of sanitary ceramic, tableware ceramic and the like.

The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.

The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings, and equivalents thereof fall within the scope of the present application. It should also be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.

Claims

1. The preparation method of the high-temperature-resistant nano antibacterial agent is characterized by comprising the following steps of:

mixing natural ore powder and water to prepare a mixture A;

mixing the mixture A with a dispersing agent to prepare a mixture B;

the natural ore powder is selected from one or more of quartz powder, talcum powder, calamine powder, shell powder, limestone powder and feldspar powder;

the dispersing agent is one or more selected from chitosan, methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose and polyvinyl alcohol;

the average particle diameter of the natural ore nano particles contained in the high-temperature resistant nano antibacterial agent is 3nm-35nm, and the particle diameter range is 1nm-50nm;

(1) The mass ratio of the natural ore powder to the water is 1: (100-200);

(2) The mass ratio of the mixture A to the dispersing agent is 1: (0.5-2);

(3) The mass ratio of the mixture B to the zirconia balls is 1: (2-4);

or alternatively, the process may be performed,

(1) The mass ratio of the natural ore powder to the water is 1: (75-150);

(2) The mass ratio of the mixture A to the dispersing agent is 1: (0.5-1.5);

(3) The mass ratio of the mixture B to the agate balls is 1: (2-6);

2. The method for preparing a high temperature resistant nano-antibacterial agent according to claim 1, wherein the diameter of the zirconia balls is 0.1mm to 0.5mm.

3. The method for preparing a high temperature resistant nano-antibacterial agent according to claim 1, wherein the diameter of the agate sphere is 0.1cm to 2cm.

4. A high temperature resistant nano-antibacterial agent, characterized in that the high temperature resistant nano-antibacterial agent is prepared by the preparation method of any one of claims 1 to 3.

5. An antimicrobial ceramic article, wherein the glaze layer of the antimicrobial ceramic article comprises a glaze and the high temperature resistant nano antimicrobial agent of claim 4.

6. The antimicrobial ceramic article of claim 5, wherein the mass ratio of the glaze to the high temperature resistant nano antimicrobial agent is 1: (0.001-0.15).

7. The method of making an antimicrobial ceramic article according to claim 5 or 6, comprising the steps of:

8. The method of preparing an antimicrobial ceramic article according to claim 7, wherein the firing conditions comprise: the temperature is 1200-1300 ℃ and the time is 2-6 h.

9. The method of producing an antimicrobial ceramic article according to claim 7 or 8, wherein the thickness of the antimicrobial glaze layer is 0.5cm to 0.9cm.