阅读说明：本技术 一种白色抗菌陶瓷及其制备方法 (White antibacterial ceramic and preparation method thereof ) 是由 林美灵 王键 黄小杰 谢祯瀛 陈招娣 洪立昕 于 2021-01-19 设计创作，主要内容包括：本发明提供了一种白色抗菌陶瓷的制备方法,包括以下步骤：将基础陶瓷进行预热后,放入熔融态铜离子抗菌熔盐中进行离子交换,冷却,得到白色抗菌陶瓷；铜离子抗菌熔盐的组分及其质量百分比为：CuSO-440％-80％、Na-2SO-410％-30％、K-2SO-410％-30％；所述离子交换温度为440-560℃,离子交换时间为20-60min；所述基础陶瓷的组成包括：SiO-2、Al-2O-3、Na-2O、K-2O、B-2O-3、CaO、ZnO；其中Na-2O的质量百分比含量为0.3-1.0％；K-2O的质量百分比含量为0-5％。通过过将含Na-2O和K-2O的基础白色陶瓷浸渍于硫酸铜、硫酸钠与硫酸钾的混合熔盐中,使陶瓷表面获得铜离子,使耐磨性及维氏硬度增强,其具有抗菌性能,抗菌活性值R≥3,并且抗菌前后△E≤1。(The invention provides a preparation method of white antibacterial ceramic, which comprises the following steps: preheating the basic ceramic, then putting the basic ceramic into molten copper ion antibacterial molten salt for ion exchange, and cooling to obtain white antibacterial ceramic; the copper ion antibacterial molten salt comprises the following components in percentage by mass: CuSO 4 40％‑80％、Na 2 SO 4 10％‑30％、K 2 SO 4 10% -30%; the ion exchange temperature is 440-560 ℃, and the ion exchange time is 20-60 min; the composition of the base ceramic comprises: SiO 2 2 、Al 2 O 3 、Na 2 O、K 2 O、B 2 O 3 CaO, ZnO; wherein Na 2 The content of O in percentage by mass is 0.3-1.0%; k 2 The content of O is 0-5% by mass. By adding Na 2 O and K 2 Soaking the basic white ceramic of O in molten salt of copper sulfate, sodium sulfate and potassium sulfate to make itThe ceramic surface obtains copper ions, so that the wear resistance and the Vickers hardness are enhanced, the ceramic has antibacterial performance, the antibacterial activity value R is more than or equal to 3, and the delta E before and after the antibacterial action is less than or equal to 1.)

1. A preparation method of white antibacterial ceramic is characterized by comprising the following steps:

preheating the basic ceramic, then putting the basic ceramic into molten copper ion antibacterial molten salt for ion exchange, and cooling to obtain the white antibacterial ceramic;

the copper ion antibacterial molten salt comprises the following components in percentage by mass: CuSO₄ 40％-80％、Na₂SO₄10％-30％、K₂SO₄10% -30%; the ion exchange temperature is 440-560 ℃, and the ion exchange time is 20-60 min;

the composition of the base ceramic comprises: SiO 2₂、Al₂O₃、Na₂O、K₂O、B₂O₃CaO, ZnO; wherein Na₂The content of O in percentage by mass is 0.3-1.0%; k₂The content of O is 0-5% by mass.

2. The preparation method according to claim 1, wherein the base ceramic comprises the following components in percentage by mass: SiO 2₂ 48％-70％、Al₂O₃ 9％-17％、ZrO₂ 0-12％、BaO 0-3％、CaO 1-12％、ZnO 0.1-7％、ZrO₂ 0-12％、MgO 0-2.5％、P₂O₅ 0％-3.0％、Na₂O 0.3-1.0％、K₂O 0-5％。

3. The preparation method of the white antibacterial ceramic according to claim 1, wherein the antibacterial molten salt comprises the following components in percentage by mass: CuSO₄ 50％-60％、Na₂SO₄ 20％-30％、K₂SO₄20% -30%; the ion exchange time is 20-30 min.

4. The method of claim 1, wherein Δ E of the white antimicrobial ceramic is 1 or less and the base ceramic before ion-exchange.

5. A white antibacterial ceramic, characterized in that, the white antibacterial ceramic is prepared by the preparation method of any one of claims 1 to 4; the antibacterial ions in the white antibacterial ceramic are copper ions.

6. The white antibacterial ceramic of claim 5, wherein the content of copper ions in the white antibacterial ceramic is 0.01-0.05% by mass.

7. The white antibacterial ceramic of claim 6, wherein the mass percentage content of copper ions in the white antibacterial ceramic is 0.01% -0.02%.

8. The white antimicrobial ceramic of claim 5, wherein the white antimicrobial ceramic has an antimicrobial R value > 3.

9. The white antibacterial ceramic according to claim 5, wherein the temperature difference of the instant change resistance of the white antibacterial ceramic is not less than 150 ℃.

Technical Field

The invention relates to the field of ceramic manufacturing, in particular to a white antibacterial ceramic and a preparation method thereof.

Background

The ceramic product has the advantages of metal strength, abundant decorative effect, good wear resistance and chemical stability, is widely used in daily life of people, and is popular with people. With the development of economy and the improvement of the living standard of people, the quality requirement of people on life is higher and higher. The consumer has continuously raised requirements for the performance of domestic ceramics, sanitary ceramics and architectural ceramics, and not only the products are required to be beautiful, practical and wear-resistant, but also the products are required to have the functions of environmental protection and health, and the demands of people on antibacterial materials and antibacterial products are increasingly strong.

At present, most of the antibacterial daily-use ceramics used by the public are white or milky ceramics, and the antibacterial function of the antibacterial daily-use ceramics is realized mainly by virtue of antibacterial glaze. Currently, the main antibacterial agents used in glazes are silver systems, copper systems and photocatalytic antibacterial agents; the traditional silver and copper antibacterial agent has the advantages that the traditional silver and copper antibacterial agent can be directly added into high-temperature ceramic glaze, the use is convenient, but the cost of the silver antibacterial agent is high, and white products are easy to turn yellow; although the cost of the copper antibacterial agent is low, the copper antibacterial agent can affect the color development of glaze materials, and is not widely used, particularly as an antibacterial agent for light-color ceramics, particularly white ceramics.

Disclosure of Invention

Therefore, it is desirable to provide a white antibacterial ceramic using copper ions as an antibacterial agent at a low cost and a method for preparing the same.

In order to achieve the above object, a first aspect of the present invention provides a method for preparing a white antibacterial ceramic, comprising the steps of:

preheating the basic ceramic, then putting the basic ceramic into molten copper ion antibacterial molten salt for ion exchange, and cooling to obtain the white antibacterial ceramic;

the copper ion antibacterial molten salt comprises the following components in percentage by mass: CuSO₄ 40％-80％、Na₂SO₄ 10％-30％、K₂SO₄10% -30%; the ion exchange temperature is 440-560 ℃, and the ion exchange time is 20-60 min;

the composition of the base ceramic comprises: SiO 2₂、Al₂O₃、Na₂O、K₂O、B₂O₃CaO, ZnO; wherein Na₂The content of O in percentage by mass is 0.3-1%; k₂The content of O is 0-5% by mass. Preferably, the composition and mass percentage of the base ceramic are SiO₂ 48％-70％、Al₂O₃ 9％-17％、ZrO₂ 0-12％、BaO 0-3％、CaO 1-12％、ZnO 0.1-7％、ZrO₂0-12％、MgO 0-2.5％、P₂O₅ 0％-3.0％、Na₂O 0.3-1％、K₂O 0-5％。

Preferably, the antibacterial molten salt comprises the following components in percentage by mass: CuSO₄ 50％-60％、Na₂SO₄ 20％-30％、K₂SO₄20% -30%; the ion exchange time is 20-30 min.

Preferably, the white antibacterial ceramic has a Delta E less than or equal to 1 with the base ceramic before ion exchange.

In a second aspect of the present invention, a white antibacterial ceramic is provided, which is prepared by the preparation method of the first aspect of the present invention; the antibacterial ions in the white antibacterial ceramic are copper ions.

Preferably, the mass percentage content of copper ions in the white antibacterial ceramic is 0.01-0.05%.

Preferably, the mass percentage content of copper ions in the white antibacterial ceramic is 0.01-0.02%.

Preferably, the antibacterial R value of the white antibacterial ceramic is more than 3.

Preferably, the temperature difference of the instant heating resistance of the white antibacterial ceramic is more than or equal to 150 ℃.

Different from the prior art, the technical scheme at least comprises the following beneficial effects: by passing Na over₂The content of O in percentage by mass is 0.3-1%; k₂The basic white ceramic with the content of 0-5% by mass of O is immersed in the mixed molten salt of copper sulfate, sodium sulfate and potassium sulfate, so that copper ions are obtained on the surface of the ceramic, the wear resistance and the Vickers hardness are enhanced, the ceramic has antibacterial performance, the antibacterial activity value R is more than or equal to 3, and the delta E before and after antibacterial is less than or equal to 1.

Drawings

FIG. 1 is a photograph of a ceramic surface that was not subjected to a wear test;

FIG. 2 is a photograph showing the surface abrasion of a sample after the base ceramic 1 not subjected to ion exchange is subjected to an abrasion resistance test;

FIG. 3 is a photograph showing the surface wear of the sample after the base ceramic 1 (example 1) was subjected to the wear resistance test after ion exchange;

FIG. 4 is a photograph showing the surface wear of a sample after the base ceramic 2 which has not been ion-exchanged has been subjected to a wear resistance test;

FIG. 5 is a photograph showing the surface wear of the sample after the base ceramic 2 (example 1) has been subjected to the wear resistance test after ion exchange;

FIG. 6 is a photograph showing the surface wear of a sample after the wear resistance test of the base ceramic 3 without ion exchange;

FIG. 7 is a photograph showing the surface wear of the sample after the base ceramic 3 (example 1) was subjected to the wear resistance test after ion exchange.

Detailed Description

To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.

Examples 1-7 of the invention were prepared by the following method:

1. preparing base ceramics: uniformly mixing the ceramic raw materials in proportion: the water ratio is 1:0.7, the ball milling fineness is 250 meshes, the mixture is sieved and glazed, and the glaze surface is put into a kiln for heat treatment after being dried, the firing temperature is 1150-1300 ℃, and the firing time is 5-8 h.

In each example, three different ceramics were used as base ceramics, respectively:

the base ceramic 1 comprises the following components in percentage by weight: SiO 2₂ 64.17％，Al₂O₃ 14.66％，ZrO₂ 11.17％，BaO 2.6％，CaO 1.91％，ZnO 1.86％，MgO 0.83％，P₂O₅ 0.85％，Na₂O 0.45％，K₂O 0.41％，

The base ceramic 2 comprises the following components in percentage by weight: SiO 2₂ 59.08％，Al₂O₃ 16.87％，CaO 11.93％，ZnO 3.02％，MgO 2.21％，P₂O₅ 0.25％，Na₂O 0.60％，K₂O 4.34％，BaO 1.7％；

Base ceramic 3 (comparative) with a composition of: SiO 2₂ 61.92％，Al₂O₃ 13.68％，Na₂O 12.95％，K₂O 4.74％，CaO 1.93％，ZnO 3.52％，MgO 1.21％。

2. Preparation of molten salt: mixing CuSO₄、Na₂SO₄、K₂SO₄Weighing according to the proportion shown in Table 1 and mixing uniformly; the melting point T0 of the antibacterial molten salt with different proportions is shown in Table 1;

placing the uniformly mixed molten salt into an alumina crucible, placing the alumina crucible into a high-temperature furnace, and melting the molten salt within the range of 440-530 ℃ for later use after the molten salt is molten;

3. ion exchange: the basic ceramic is placed in a preheating furnace to be preheated for 30min, the preheating temperature T1 and the molten salt temperature T2 need to be controlled to be T2-T1 less than 100 ℃, the preheated basic ceramic is placed in molten antibacterial molten salt to carry out ion exchange, and the exchange time and the exchange temperature are shown in table 1. And after finishing ion exchange, putting the ceramic into a muffle furnace for rapid cooling to obtain the antibacterial ceramic, cleaning residues on the surface of the antibacterial ceramic by using hot water, and carrying out performance test, wherein test items and results are shown in table 1.

The basic ceramic is firstly tested according to QB/T1503-2011, and then the antibacterial ceramic after ion exchange is tested according to La-b, and delta E is calculated, and the color difference judgment is carried out according to GB/T3532-1995, and the result is shown in Table 1.

Table 1 compositions, processes and performance tables for antibacterial ceramics prepared in examples 1-7

Examples 1-7 test items physical properties the definition and explanation or test methods are as follows:

(1) melting point T0: indicating the temperature of the high-temperature furnace after the mixed molten salt is completely melted;

(2) molten salt temperature T2: setting the temperature of ion exchange, and indicating the temperature of a high-temperature furnace;

(3) cu content: testing by adopting a handheld XRF;

(4)L^*a^*b^*the value: the reflectivity is tested by adopting an Shimadzu UV-2600 ultraviolet spectrophotometer, and the L is obtained by converting the instrument with software' color anyist^*Value a^*Value b^*A value;

(5) delta E: according to QB/T1503 and 2011,

△E＝【(△L^*)²+(△a^*)²+(△b^*)²】^1/2

(6) antibacterial activity value R: according to the method in JIS Z2081:2010, test bacterial liquid is inoculated on a basic ceramic plate and an antibacterial ceramic plate, the ceramic plate is cultured for 24H in an aseptic plate, the average logarithmic value of the viable count obtained by culturing the ceramic plate for 24H is calculated, and the average logarithmic difference value of the viable count is calculated.

From the data in table 1, it can be seen that the temperature of the molten salt (ion exchange) has a significant effect on the effect of the ion exchange in examples 3 and 4. And the basic ceramic material has high Na and K contents, so that the ion exchange is more, the Cu content in the antibacterial ceramic is too high, the Delta E is more than 1, and the color of the ceramic has color difference.

And (3) wear resistance test:

equipment: an abrasion resistance tester, model A20-339, the revolution range is 0-3000, the fineness of abrasive paper is 150 meshes, and the sample size is phi 35 mm; the working temperature of the drying box is 110 +/-5 ℃; an electronic balance, accurate to 0.0001 g;

the test steps are as follows: weighing m1 before and after the antibacterial test piece, then placing the test piece on a sample table with the surface facing upwards, clamping the test piece by using a metal clamp, installing 150-mesh abrasive paper on a grinding head, enabling the abrasive paper on the grinding head to be in contact with the test piece, simultaneously selecting a load of 500g to be loaded on the grinding head, setting the revolution number of 500, and starting an instrument. Immediately stopping the machine when the grinding is carried out for the set times, taking down the test piece, washing the test piece by flowing water, drying the test piece in a drying box, weighing the test piece by using a balance m2, calculating the mass loss before and after grinding, and observing the surface abrasion condition by using a microscope, wherein the specific figures are shown in figures 1-7.

The vickers hardness and abrasion resistance results for examples 1-7 are shown in table 2,

TABLE 2 comparison of Vickers hardness and abrasion resistance of basic ceramics (before ion exchange) and antibacterial ceramics (after antibacterial)

Vickers hardness number: a Vickers hardness tester, model TMVP-1S, a diamond pressure head, a load of 300g and a load time of 15S.

As can be seen from FIGS. 1 to 7 and Table 2, base ceramic 1 (Na)₂O 0.45％，K₂O0.41%) and base ceramic 2 (Na)₂O 0.60％，K₂Na in O4.34%,)₂The content of O is less than 1 percent, the Vickers hardness is higher, and the wear-resisting condition is better than that of the basic ceramic 3; and base ceramic 3 (Na)₂O 12.95％，K₂O4.74%) of Na₂The content of O is high, and the component Na in the ceramic is found in research₂The content of O is more than 1%, and the thermal expansion coefficient of the ceramic is increasedHigh, thermal stability, chemical stability and mechanical strength are all reduced. Thereby controlling Na in the base ceramic₂The content of O in percentage by mass is 0.3-1.0%; k₂The content of O in percentage by mass is 0-5%, which is beneficial to controlling the content of copper ions entering the ceramic in the later period to be 0.01-0.05 wt%, when the copper content on the surface of the ceramic is more than 0.01%, the R value is more than 3 with good antibacterial effect, and the appearance of the product is discolored due to the introduction of excessive copper ions into the ceramic.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.

It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.