CN109896839B - Antibacterial and mildewproof ceramic tile and preparation method thereof - Google Patents
Antibacterial and mildewproof ceramic tile and preparation method thereof Download PDFInfo
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- CN109896839B CN109896839B CN201910333470.2A CN201910333470A CN109896839B CN 109896839 B CN109896839 B CN 109896839B CN 201910333470 A CN201910333470 A CN 201910333470A CN 109896839 B CN109896839 B CN 109896839B
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Abstract
The invention provides an antibacterial mildew-proof ceramic tile and a preparation method thereof. The method comprises the following steps: pressing and molding the blank material to obtain a ceramic tile blank; spraying glaze on the surface of the ceramic tile blank, and sintering to obtain a ceramic tile blank; and (3) carrying out post-treatment on the ceramic tile adobe by adopting a solution containing an antibacterial agent to obtain the antibacterial and mildewproof ceramic tile. The invention takes silver oxide and rare earth metal oxide as ceramic tile glaze components, and silver oxide particles are fixed by forming a stable compound, so that silver loss in the using process is avoided; by adding the antibacterial agent into the antibacterial ceramic tile glaze layer, negative silver ions with excellent bactericidal property are formed, and the negative silver ions are used as a photocatalyst to participate in the generation of various antibacterial groups, so that the antibacterial durability of the surface of the ceramic tile is guaranteed.
Description
Technical Field
The invention belongs to the technical field of ceramic processing, and relates to an antibacterial and mildewproof ceramic tile and a preparation method thereof.
Background
The ceramic tile is an important ceramic product, is mainly a building or decoration material obtained by grinding, mixing, pressing, glazing, sintering and other processes of metal oxide and semimetal oxide, and when the ceramic tile is applied to places such as hospitals, restaurants and the like, and occasions such as kitchens, toilets and the like in families, the traditional ceramic tile does not have the functions of decontamination, deodorization, sterilization and self-cleaning, and can bring harm to human health, so that the ceramic tile with the functions of antibiosis, mildew prevention and self-cleaning is produced.
The antibacterial ceramic tile is a product combining a ceramic technology and an antibacterial technology, maintains the original functions and decoration effects of the ceramic product, simultaneously increases the functions of disinfection, sterilization and mildew resistance, and has wider application. The existing antibacterial ceramic tile is generally added with silver nano materials on the basis of common ceramic tiles, and the main antibacterial function of the existing antibacterial ceramic tile is the antibacterial nano material on the surface layer, if the existing antibacterial ceramic tile is added into ceramic raw materials, the effect of the existing antibacterial ceramic tile cannot be fully exerted, but if the existing antibacterial ceramic tile is directly added into the surface layer, the existing antibacterial ceramic tile is easy to gradually fall off along with the prolonging of the service time and loses the antibacterial function; meanwhile, when the nano silver material is used alone, agglomeration is easy to occur, and the antibacterial effect is poor. In this regard, researchers have also made various improvements.
CN 102765930A discloses a method for manufacturing an antibacterial ceramic tile, which comprises the steps of preparing a blank by taking kaolin, feldspar and porcelain clay as raw materials, imprinting a latticed wire groove formed by vertically crossing horizontal and vertical lines on one surface of the blank of the ceramic tile, placing nano silver wires in the wire groove, preparing glaze slurry by using diatomite powder, quartz stone powder, metal silver powder and color powder, glazing the blank of the ceramic tile, and firing to form the antibacterial ceramic tile. CN 109293338A discloses an anion antibacterial ceramic tile and a production process thereof, wherein the antibacterial ceramic tile comprises a blank body, a ground glaze and a surface glaze, the blank body comprises clay, sand, ceramic tile waste, broken clay powder, diatomite and functional fiber cloth, the ground glaze and the surface glaze both comprise clay, feldspar, quartz, nano silver, nano titanium dioxide and the like, the antibacterial function is activated by means of moisture and air in holes of the blank body, but the antibacterial function of the antibacterial ceramic tile is still difficult to maintain for a long time.
In summary, the existing antibacterial and mildewproof ceramic tiles still have the problems of unstable antibacterial performance, difficulty in lasting and high cost, and an environment-friendly antibacterial and mildewproof ceramic tile with low cost and stable antibacterial property is urgently needed to be developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an antibacterial and mildewproof ceramic tile and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides an antibacterial and mildewproof ceramic tile which comprises a blank material, a glaze and an antibacterial agent, wherein the glaze comprises feldspar, alkaline earth metal carbonate, silver oxide and rare earth metal oxide, and the antibacterial agent comprises nano zinc oxide.
The antibacterial ceramic tile mainly comprises a blank material, a glaze material and an antibacterial agent in composition, and structurally comprises the blank and a glaze material layer on the surface of the blank, wherein the antibacterial agent is added into the glaze material layer; the glaze comprises silver oxide and rare earth metal oxide, and the silver oxide and the rare earth metal oxide can form a stable compound in the preparation process, so that silver oxide particles are fixed, and the loss in the use process is avoided; the glaze layer is added with the antibacterial agent, and the generated free electrons are captured by rare earth metal and then supplied to silver by utilizing the photocatalysis characteristic of the nano zinc oxide to form negative silver ions, so that the glaze layer has strong sterilization and mildew resistance effects and strong durability.
In addition, the nano zinc oxide can react with oxygen and moisture in the air under illumination to generate antibacterial substances such as oxygen atoms, hydroxyl radicals, negative oxygen ions and the like, and guarantee is provided for the antibacterial durability of the surface of the ceramic tile.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferable embodiment of the present invention, the feldspar comprises potassium feldspar.
Preferably, the alkaline earth metal carbonate comprises calcium carbonate and/or barium carbonate.
Preferably, the rare earth metal oxide comprises terbium oxide.
In the invention, when the rare earth metal is terbium, the net-shaped Ag can be formed in the glaze layer after sintering51Tb14The compound has stable property, is beneficial to the fixation of silver in a glaze layer, and the outermost layer of terbium atoms has a valence electron band which is not filled with electrons, has more electron holes, can capture free electrons generated in the photocatalysis process, and is further captured by silver atoms to form negative valence silver ions, so that the glaze layer on the surface of the ceramic tile has excellent bactericidal property.
Preferably, the glaze comprises the following components in parts by weight: 30.7-39.4 parts of feldspar, such as 30.7 parts, 32.0 parts, 34.0 parts, 36.0 parts, 38.0 parts or 39.4 parts; 47.5 to 70.1 parts of alkaline earth metal carbonate, such as 47.5 parts, 50.0 parts, 55.0 parts, 60.0 parts, 65.0 parts or 70.1 parts; 3.7-5.3 parts of silver oxide, such as 3.7 parts, 4.0 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5.0 parts or 5.3 parts; 0.8-1.5 parts of rare earth metal oxide, such as 0.8 part, 0.9 part, 1.0 part, 1.1 part, 1.2 parts, 1.3 parts, 1.4 parts or 1.5 parts; the choice of the parts by weight is not restricted to the cited values, but other values not cited within the respective numerical range are likewise suitable.
Preferably, the alkaline earth metal carbonate comprises 20.4 to 34.8 parts by weight of calcium carbonate, for example 20.4 parts, 22.5 parts, 25.0 parts, 27.0 parts, 30.0 parts, 32.0 parts or 34.8 parts, but not limited to the recited values, and other values not recited within the range of values are also applicable; the barium carbonate is 27.1 to 35.3 parts by weight, for example, 27.1 parts, 28.5 parts, 30.0 parts, 32.0 parts, 34.0 parts or 35.3 parts by weight, but is not limited to the enumerated values, and other values not enumerated within the range of the enumerated values are also applicable.
Preferably, the antimicrobial agent further comprises a sol, preferably a silica sol.
In the invention, in order to ensure that the nano zinc oxide can stably exist in the glaze layer, the sol and the glaze are commonly used together, and the nano zinc oxide and the glaze are better combined by utilizing the high dispersibility of the sol solution and the high adhesiveness after the solvent is removed, so that the loss of the antibacterial agent in the using process is avoided, and the migration and the transfer of free electrons are also facilitated.
Preferably, the mass percentage of the nano zinc oxide in the antibacterial agent is 37.6 to 51.1 wt%, such as 37.6 wt%, 40.0 wt%, 42.0 wt%, 44.0 wt%, 46.0 wt%, 48.0 wt%, 50.0 wt% or 51.1 wt%, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the nano zinc oxide is in a needle structure.
Preferably, the antibacterial agent accounts for 21 to 28 wt% of the glaze, such as 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt% or 28 wt%, but not limited to the enumerated values, and other non-enumerated values within the range are also applicable.
As a preferable technical scheme of the invention, the blank material comprises kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz.
Preferably, the blank material comprises the following components in parts by weight: 12.0-35.4 parts of kaolin, such as 12.0 parts, 15.0 parts, 20.0 parts, 25.0 parts, 30.0 parts or 35.4 parts; 11.2-18.7 parts of feldspar, such as 11.2 parts, 12.0 parts, 14.0 parts, 16.0 parts, 18.0 parts or 18.7 parts; 12.5-19.7 parts of calcined talc, such as 12.5 parts, 14.0 parts, 16.0 parts, 18.0 parts or 19.7 parts; 15.7-22.4 parts of ceramic tile waste, such as 15.7 parts, 17.0 parts, 18.0 parts, 20.0 parts, 21.0 parts or 22.4 parts; 2.2-5.7 parts of diatomite, such as 2.2 parts, 3.0 parts, 4.0 parts, 5.0 parts or 5.7 parts; 19.9 to 23.6 parts of quartz, such as 19.9 parts, 20.5 parts, 21.0 parts, 22.0 parts, 23.0 parts or 23.6 parts; the choice of the parts by weight is not restricted to the cited values, but other values not cited within the respective numerical range are likewise suitable.
Preferably, the glaze accounts for 13 to 16 wt% of the green body material, such as 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, or 16 wt%, but not limited to the recited values, and other values in the range of the recited values are also applicable.
In another aspect, the invention provides a preparation method of an antibacterial and mildewproof ceramic tile, which comprises the following steps:
(1) pressing and molding the blank material to obtain a ceramic tile blank;
(2) spraying glaze on the surface of the ceramic tile blank obtained in the step (1) and then sintering to obtain a ceramic tile blank;
(3) and (3) carrying out post-treatment on the ceramic tile adobe obtained in the step (2) by adopting a solution containing an antibacterial agent to obtain the antibacterial and mildewproof ceramic tile.
According to the invention, the ceramic tile blank after being sprayed with the glaze is sintered to obtain a stable compound in the glaze layer of the ceramic tile blank, so that the loss of antibacterial components is avoided, the antibacterial durability is enhanced, and then the antibacterial agent is infiltrated into the ceramic tile glaze layer through post-treatment to serve as a photocatalyst to provide free electrons and antibacterial substances for the antibacterial and mildew-proof of the ceramic tile.
As a preferable technical scheme of the invention, the blank material in the step (1) is prepared by mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz in parts by weight, ball-milling, spraying granulation and ageing.
Preferably, the pressure for the press forming in step (1) is 350 to 380MPa, such as 350MPa, 355MPa, 360MPa, 365MPa, 370MPa, 375MPa or 380MPa, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferable technical scheme of the invention, the glaze in the step (2) is slurry glaze obtained by mixing feldspar, alkaline earth metal carbonate, silver oxide and rare earth metal oxide in parts by weight and performing ball milling.
Preferably, the thickness of the glaze sprayed on the surface of the tile blank is 0.5-1.0 mm, such as 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm or 1.0mm, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the sintering temperature in step (2) is 1300-1400 ℃, such as 1300 ℃, 1320 ℃, 1340 ℃, 1350 ℃, 1360 ℃, 1380 ℃ or 1400 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sintering time in step (2) is 1-2 h, such as 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sintering of step (2) is performed under vacuum conditions or in a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen and/or an inert gas.
As a preferable technical scheme of the invention, the sintering in the step (2) is cooled and polished.
Preferably, the pressure of the polishing treatment is 1.5 to 2.0MPa, such as 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2.0MPa, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, after the sintered ceramic tile adobe is naturally cooled, the pressure polishing treatment is carried out by adopting the polishing solution under the pressure.
As a preferable technical scheme of the invention, the antibacterial agent in the step (3) comprises nano zinc oxide and sol.
Preferably, the post-treatment of step (3) comprises surface antifouling treatment and surface ultra-clean treatment in sequence;
preferably, the surface antifouling treatment is carried out in an antifouling treatment liquid having an antibacterial agent content of 28 to 35g/L, for example, 28g/L, 29g/L, 30g/L, 32g/L, 34g/L, 35g/L, etc., but not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the surface ultra-bright treatment is performed in an ultra-bright treatment solution, wherein the antibacterial agent content in the ultra-bright treatment solution is 28-35 g/L, such as 28g/L, 29g/L, 30g/L, 32g/L, 34g/L or 35g/L, but not limited to the recited values, and other values not recited in the numerical value range are also applicable.
As a preferable technical scheme of the invention, after the post-treatment in the step (3), edging, chamfering, cleaning and drying are carried out to obtain the antibacterial and mildewproof ceramic tile.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz in parts by weight, ball-milling, spraying, granulating and ageing to obtain a blank material, and pressing and molding the blank material under the pressure of 350-380 MPa to obtain a ceramic tile blank;
(2) spraying slurry glaze obtained by mixing and ball-milling feldspar, alkaline earth metal carbonate, silver oxide and rare earth metal oxide according to parts by weight on the surface of the ceramic tile blank obtained in the step (1), wherein the thickness of the sprayed glaze is 0.5-1.0 mm, and then sintering at the sintering temperature of 1300-1400 ℃ for 1-2 hours to obtain a ceramic tile green brick;
(3) and (3) cooling the tile adobe obtained in the step (2), then polishing at the pressure of 1.5-2.0 MPa, then sequentially carrying out surface antifouling treatment by adopting an antifouling treatment solution and surface ultraclean treatment by adopting an ultraclean treatment solution, wherein the content of an antibacterial agent in the used solution is independently 28-35 g/L, and the antibacterial agent comprises nano titanium dioxide and sol, and then edging, chamfering, cleaning and drying to obtain the antibacterial and mildewproof tile.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the antibacterial mildew-proof ceramic tile takes the silver oxide and the rare earth metal oxide as glaze components, and silver oxide particles are fixed by forming a stable compound, so that silver loss in the using process is avoided;
(2) according to the invention, the antibacterial agent is added into the antibacterial ceramic tile glaze layer, free electrons are continuously provided in the photocatalysis process, negative silver ions are finally formed, the antibacterial agent has excellent bactericidal property, and can react with oxygen in the air and water molecules to generate a plurality of antibacterial groups as a photocatalyst, the bactericidal rate is up to more than 99.96%, and the antibacterial durability of the surface of the ceramic tile is also guaranteed;
(3) the antibacterial agent is added in the post-treatment process of the ceramic tile preparation, so that the operation steps are simplified, and meanwhile, the waste ceramic tile can be reused as a blank raw material, so that the waste utilization is realized, and the cost of the antibacterial ceramic tile is reduced.
Drawings
Fig. 1 is a process flow chart of a method for preparing the antibacterial and mildewproof ceramic tile provided by embodiment 1 of the invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides an antibacterial and mildewproof ceramic tile and a preparation method thereof.
The method comprises the following steps:
(1) pressing and molding the blank material to obtain a ceramic tile blank;
(2) spraying glaze on the surface of the ceramic tile blank obtained in the step (1) and then sintering to obtain a ceramic tile blank;
(3) and (3) carrying out post-treatment on the ceramic tile adobe obtained in the step (2) by adopting a solution containing an antibacterial agent to obtain the antibacterial and mildewproof ceramic tile.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides an antibacterial and mildewproof ceramic tile and a preparation method thereof, wherein the antibacterial and mildewproof ceramic tile comprises a blank material, a glaze material and an antibacterial agent;
wherein the blank material comprises the following components in parts by weight: 26.6 parts of kaolin, 12.7 parts of feldspar, 12.5 parts of calcined talc, 22.4 parts of ceramic tile waste, 2.2 parts of diatomite and 23.6 parts of quartz;
the glaze comprises the following components in parts by weight: 30.7 parts of potassium feldspar, 34.8 parts of calcium carbonate, 29.6 parts of barium carbonate, 4.1 parts of silver oxide and 0.8 part of terbium oxide, wherein the glaze accounts for 16 wt% of the blank material;
the antibacterial agent comprises nanometer zinc oxide and silica sol, wherein the mass percent of the nanometer zinc oxide is 37.6 wt%, and the mass percent of the antibacterial agent in the glaze is 21 wt%.
The process flow diagram of the method is shown in figure 1, and comprises the following steps:
(1) mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz according to the above weight parts, performing wet ball milling, performing spray granulation, and aging to obtain a blank material, and performing compression molding under the pressure of 350MPa to obtain a ceramic tile blank;
(2) spraying slurry glaze obtained by mixing and ball-milling potassium feldspar, calcium carbonate, barium carbonate, silver oxide and terbium oxide according to the weight parts on the surface of the ceramic tile blank obtained in the step (1), wherein the thickness of the sprayed glaze is 0.5mm, and then sintering at 1300 ℃ for 2 hours to obtain a ceramic tile blank;
(3) and (3) cooling the ceramic tile adobe obtained in the step (2), then polishing at the pressure of 1.5MPa, then sequentially carrying out surface antifouling treatment by adopting an antifouling treatment liquid and surface ultraclean treatment by adopting an ultraclean treatment liquid, wherein the addition amount of the antibacterial agent in the used solution is 28g/L, and then carrying out edging, chamfering, cleaning and drying to obtain the antibacterial and mildewproof ceramic tile.
Example 2:
the embodiment provides an antibacterial and mildewproof ceramic tile and a preparation method thereof, wherein the antibacterial and mildewproof ceramic tile comprises a blank material, a glaze material and an antibacterial agent;
wherein the blank material comprises the following components in parts by weight: 35.4 parts of kaolin, 11.2 parts of feldspar, 14.3 parts of calcined talc, 15.7 parts of ceramic tile waste, 3.5 parts of diatomite and 19.9 parts of quartz;
the glaze comprises the following components in parts by weight: 39.4 parts of potassium feldspar, 20.4 parts of calcium carbonate, 35.3 parts of barium carbonate, 3.7 parts of silver oxide and 1.2 parts of terbium oxide, wherein the glaze accounts for 15 wt% of the blank material;
the antibacterial agent comprises nano zinc oxide and silica sol, wherein the mass percent of the nano zinc oxide is 44.2 wt%, and the antibacterial agent accounts for 24 wt% of the glaze.
The method comprises the following steps:
(1) mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz according to the above weight parts, performing wet ball milling, performing spray granulation, and aging to obtain a blank material, and performing compression molding under 365MPa to obtain a ceramic tile blank;
(2) spraying slurry glaze obtained by mixing and ball-milling potassium feldspar, calcium carbonate, barium carbonate, silver oxide and terbium oxide according to the weight parts on the surface of the ceramic tile blank obtained in the step (1), wherein the thickness of the sprayed glaze is 0.7mm, and then sintering at 1350 ℃ for 1.5h to obtain a ceramic tile blank;
(3) and (3) cooling the ceramic tile adobe obtained in the step (2), then polishing at the pressure of 1.8MPa, then sequentially carrying out surface antifouling treatment by adopting an antifouling treatment liquid and surface ultraclean treatment by adopting an ultraclean treatment liquid, wherein the addition amount of the antibacterial agent in the used solution is 30g/L, and then carrying out edging, chamfering, cleaning and drying to obtain the antibacterial and mildewproof ceramic tile.
Example 3:
the embodiment provides an antibacterial and mildewproof ceramic tile and a preparation method thereof, wherein the antibacterial and mildewproof ceramic tile comprises a blank material, a glaze material and an antibacterial agent;
wherein the blank material comprises the following components in parts by weight: 12.0 parts of kaolin, 18.7 parts of feldspar, 19.7 parts of calcined talc, 17.1 parts of ceramic tile waste, 5.7 parts of diatomite and 21.8 parts of quartz;
the glaze comprises the following components in parts by weight: 35.5 parts of potassium feldspar, 30.6 parts of calcium carbonate, 27.1 parts of barium carbonate, 5.3 parts of silver oxide and 1.5 parts of terbium oxide, wherein the glaze accounts for 13 wt% of the blank material;
the antibacterial agent comprises nano zinc oxide and silica sol, wherein the mass percent of the nano zinc oxide is 51.1 wt%, and the antibacterial agent accounts for 28 wt% of the glaze.
The method comprises the following steps:
(1) mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz according to the above weight parts, performing wet ball milling, performing spray granulation, and aging to obtain a blank material, and performing compression molding under the pressure of 380MPa to obtain a ceramic tile blank;
(2) spraying slurry glaze obtained by mixing and ball-milling potassium feldspar, calcium carbonate, barium carbonate, silver oxide and terbium oxide according to the weight parts on the surface of the ceramic tile blank obtained in the step (1), wherein the thickness of the sprayed glaze is 1.0mm, and then sintering at the sintering temperature of 1400 ℃ for 1h to obtain a ceramic tile blank;
(3) and (3) cooling the ceramic tile adobe obtained in the step (2), then polishing at the pressure of 2.0MPa, then sequentially carrying out surface antifouling treatment by adopting an antifouling treatment liquid and surface ultraclean treatment by adopting an ultraclean treatment liquid, wherein the addition amount of the antibacterial agent in the used solution is 35g/L, and then carrying out edging, chamfering, cleaning and drying to obtain the antibacterial and mildewproof ceramic tile.
Example 4:
the embodiment provides an antibacterial and mildewproof ceramic tile and a preparation method thereof, wherein the antibacterial and mildewproof ceramic tile comprises a blank material, a glaze and an antibacterial agent;
wherein the blank material comprises the following components in parts by weight: 19.6 parts of kaolin, 15.4 parts of feldspar, 17.2 parts of calcined talc, 20.3 parts of ceramic tile waste, 4.8 parts of diatomite and 22.4 parts of quartz;
the glaze comprises the following components in parts by weight: 35.5 parts of potassium feldspar, 50.4 parts of calcium carbonate, 4.8 parts of silver oxide and 1.0 part of cerium oxide, wherein the glaze accounts for 14 wt% of the blank material;
the antibacterial agent comprises 47.3 wt% of nano zinc oxide and 26 wt% of silica sol, and the mass percentage of the antibacterial agent in the glaze is.
The process is referred to the process in example 1, with the only difference that: the composition parts by weight of the green body material and the glaze material were selected in this example.
Example 5:
the present embodiment provides an antibacterial and mildewproof tile and a preparation method thereof, wherein the composition of the antibacterial and mildewproof tile is as follows: the antimicrobial agent comprises only nano zinc oxide.
The process is referred to in example 1.
Example 6:
the present embodiment provides an antibacterial and mildewproof tile and a preparation method thereof, wherein the composition of the antibacterial and mildewproof tile is as follows: the glaze comprises 5.4 parts of silver oxide and 0.7 part of terbium oxide, namely the proportion of the silver oxide to the terbium oxide is larger.
The process is referred to the process in example 1, with the only difference that: the composition parts by weight of the green body material and the glaze material were selected in this example.
Example 7:
the present embodiment provides an antibacterial and mildewproof tile and a preparation method thereof, wherein the composition of the antibacterial and mildewproof tile is as follows: the glaze comprises 3.6 parts of silver oxide and 1.6 parts of terbium oxide, namely the proportion of the silver oxide to the terbium oxide is small.
The process is referred to the process in example 2, with the only difference that: the composition parts by weight of the green body material and the glaze material were selected in this example.
Comparative example 1:
the present comparative example provides an antibacterial and mildewproof tile and a method for manufacturing the same, the composition of which is as in example 1, except that: the glaze does not contain terbium oxide, namely rare earth metal oxide, wherein the terbium oxide is proportionally distributed into other glaze compositions, and the glaze accounts for the blank material in a constant mass percentage.
The process is referred to the process in example 1, with the only difference that: the glaze components in parts by weight were selected in this comparative example.
Comparative example 2:
the present comparative example provides an antibacterial and mildewproof tile and a method for manufacturing the same, the composition of which is as in example 1, except that: the composition of the antimicrobial tile does not include an antimicrobial agent.
The process is referred to the process in example 1, with the only difference that: and (4) adding an antibacterial agent into the antifouling treatment liquid and the ultra-clean treatment liquid used in the step (3).
The antibiotic tiles prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to antibiotic experiments with escherichia coli and staphylococcus aureus, and the antibiotic effects and persistence thereof were examined, and the results are shown in table 1.
Table 1 results of the antibacterial effect and durability test of the antibacterial tiles described in examples 1 to 7 and comparative examples 1 to 2
As can be seen from Table 1, the number of bacteria in examples 1-3 is reduced to 100 or less and the minimum number is reduced to 10 or less after 168 hours under the condition that the initial number of bacteria is basically the same by taking Escherichia coli and Staphylococcus aureus as test strains, and the antibacterial effect is excellent and durable; the rare earth metal oxide used in example 4 is slightly inferior in antibacterial effect but is not much different from example 1; in example 5, since silica sol was not used, the binding effect of nano zinc oxide with the glaze was weakened, and the durability of the antibacterial property was slightly poor; in example 6, the ratio of the silver oxide to the terbium oxide is large, which not only increases the cost, but also makes the surplus silver oxide not fixed and easy to run off, which is not favorable for improving the antibacterial performance; in example 7, the ratio of the silver oxide to the terbium oxide is small, and the antibacterial effect and the durability are slightly poor; in the comparative example 1, rare earth metal oxide is not used, silver oxide cannot be fully fixed in the glaze, and the silver oxide is easy to run off in the using process, so that the durability of the antibacterial property is poor; in comparative example 2, no antibacterial agent was used as a photocatalyst, and sufficient free electrons could not be supplied to form a negative silver ion having a strong bactericidal property, and also no antibacterial group such as hydroxyl radical could be formed, resulting in poor antibacterial effect.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (28)
1. The antibacterial and mildewproof ceramic tile is characterized by comprising a blank material, a glaze and an antibacterial agent, wherein the glaze comprises the following components in parts by weight: 30.7-39.4 parts of feldspar; 47.5-70.1 parts of alkaline earth metal carbonate; 3.7-5.3 parts of silver oxide; 0.8-1.5 parts of rare earth metal oxide;
the antibacterial agent comprises nano zinc oxide;
the antibacterial agent accounts for 21-28 wt% of the glaze;
the rare earth metal oxide is terbium oxide;
the antibacterial and mildewproof ceramic tile is prepared by the following method, and the method comprises the following steps:
(1) pressing and molding the blank material to obtain a ceramic tile blank;
(2) spraying glaze on the surface of the ceramic tile blank obtained in the step (1) and then sintering to obtain a ceramic tile blank;
(3) carrying out post-treatment on the ceramic tile adobe obtained in the step (2) by adopting a solution containing an antibacterial agent to obtain an antibacterial and mildewproof ceramic tile;
the sterilization rate of the antibacterial and mildewproof ceramic tile is more than 99.96 percent.
2. The antibacterial and mildewproof ceramic tile according to claim 1, wherein the feldspar comprises potassium feldspar.
3. The antibacterial, mildewproof tile according to claim 1, wherein the alkaline earth metal carbonate comprises calcium carbonate and/or barium carbonate.
4. The antibacterial and mildewproof ceramic tile according to claim 3, wherein the alkaline earth metal carbonate comprises 20.4 to 34.8 parts by weight of calcium carbonate and 27.1 to 35.3 parts by weight of barium carbonate.
5. The antimicrobial, mold-proof tile of claim 1, wherein said antimicrobial agent further comprises a sol.
6. The antibacterial and mildewproof ceramic tile according to claim 5, wherein the sol is a silica sol.
7. The antibacterial and mildewproof ceramic tile according to claim 5, wherein the mass percent of the nano zinc oxide in the antibacterial agent is 37.6-51.1 wt%.
8. The antibacterial and mildewproof ceramic tile according to claim 1, wherein the nano zinc oxide has a needle-like structure.
9. The antibacterial and mildewproof ceramic tile according to claim 1, wherein the composition of the green body material comprises kaolin, feldspar, burnt talc, ceramic tile waste, diatomite and quartz.
10. The antibacterial and mildewproof ceramic tile according to claim 9, wherein the green body material comprises the following components in parts by weight: 12.0-35.4 parts of kaolin; 11.2-18.7 parts of feldspar; 12.5-19.7 parts of calcined talc; 15.7-22.4 parts of ceramic tile waste; 2.2-5.7 parts of diatomite; 19.9-23.6 parts of quartz.
11. The antibacterial and mildewproof ceramic tile according to claim 1, wherein the glaze accounts for 13-16 wt% of the blank material.
12. The method for manufacturing antimicrobial and mildewproof ceramic tile according to any one of claims 1 to 11, wherein the method comprises the following steps:
(1) pressing and molding the blank material to obtain a ceramic tile blank;
(2) spraying glaze on the surface of the ceramic tile blank obtained in the step (1) and then sintering to obtain a ceramic tile blank;
(3) and (3) carrying out post-treatment on the ceramic tile adobe obtained in the step (2) by adopting a solution containing an antibacterial agent to obtain the antibacterial and mildewproof ceramic tile.
13. The preparation method according to claim 12, wherein the green body material in the step (1) is prepared by mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz in parts by weight, ball milling, spray granulation and aging.
14. The production method according to claim 12, wherein the pressure for the press molding in the step (1) is 350 to 380 MPa.
15. The preparation method according to claim 12, wherein the glaze in step (2) is a slurry glaze obtained by mixing feldspar, alkaline earth metal carbonate, silver oxide and rare earth metal oxide in parts by weight and performing ball milling.
16. The preparation method of claim 12, wherein the thickness of the glaze sprayed on the surface of the tile blank is 0.5-1.0 mm.
17. The method according to claim 12, wherein the sintering temperature in the step (2) is 1300-1400 ℃.
18. The preparation method according to claim 12, wherein the sintering time in the step (2) is 1-2 h.
19. The method according to claim 12, wherein the sintering of step (2) is performed under vacuum conditions or in a protective atmosphere.
20. The method of claim 19, wherein the protective atmosphere comprises nitrogen and/or an inert gas.
21. The production method according to claim 12, wherein the step (2) is carried out by cooling after sintering and polishing.
22. The method according to claim 21, wherein the pressure of the polishing treatment is 1.5 to 2.0 MPa.
23. The method for preparing according to claim 12, wherein the antibacterial agent of step (3) comprises nano zinc oxide and sol.
24. The method according to claim 12, wherein the post-treatment of step (3) comprises a surface anti-fouling treatment and a surface ultra-clear treatment in this order.
25. The production method according to claim 24, wherein the surface antifouling treatment is performed in an antifouling treatment liquid containing 28 to 35g/L of an antibacterial agent.
26. The preparation method according to claim 24, wherein the surface ultra-bright treatment is performed in an ultra-bright treatment solution, and the content of the antibacterial agent in the ultra-bright treatment solution is 28-35 g/L.
27. The preparation method according to claim 12, wherein after the post-treatment in the step (3), the antibacterial and mildewproof ceramic tile is obtained by edging, chamfering, cleaning and drying.
28. The method for preparing according to claim 12, characterized in that it comprises the steps of:
(1) mixing kaolin, feldspar, calcined talc, ceramic tile waste, diatomite and quartz in parts by weight, ball-milling, spraying, granulating and ageing to obtain a blank material, and pressing and molding the blank material under the pressure of 350-380 MPa to obtain a ceramic tile blank;
(2) spraying slurry glaze obtained by mixing and ball-milling feldspar, alkaline earth metal carbonate, silver oxide and rare earth metal oxide according to parts by weight on the surface of the ceramic tile blank obtained in the step (1), wherein the thickness of the sprayed glaze is 0.5-1.0 mm, and then sintering at the sintering temperature of 1300-1400 ℃ for 1-2 hours to obtain a ceramic tile green brick;
(3) and (3) cooling the tile adobe obtained in the step (2), then polishing at the pressure of 1.5-2.0 MPa, then sequentially carrying out surface antifouling treatment by adopting an antifouling treatment solution and surface ultraclean treatment by adopting an ultraclean treatment solution, wherein the content of an antibacterial agent in the used solution is independently 28-35 g/L, and the antibacterial agent comprises nano titanium dioxide and sol, and then edging, chamfering, cleaning and drying to obtain the antibacterial and mildewproof tile.
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| CN113912296B (en) * | 2021-11-26 | 2023-06-06 | 亚细亚建筑材料股份有限公司 | Antibacterial mildew-proof ceramic glaze and preparation method and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7704754B2 (en) * | 2004-01-27 | 2010-04-27 | American Environmental Systems, Inc. | Method of plasmon-enhanced properties of materials and applications thereof |
| CN101744002A (en) * | 2009-12-29 | 2010-06-23 | 浙江理工大学 | Silicon-zinc mesoporous material silver-carrying antibacterial agent and preparation method thereof |
| CN104607039A (en) * | 2015-01-20 | 2015-05-13 | 济南木齐健康科技有限公司 | Composite material with anti-bacterial and purifying functions and preparation method of composite material |
| CN106348792A (en) * | 2016-08-26 | 2017-01-25 | 高名胜 | Manufacturing method of antibacterial ceramic tiles |
| CN107721369A (en) * | 2017-09-26 | 2018-02-23 | 苏州米颜生物科技有限公司 | It is a kind of non-burning brick with self-purification capacity with sterilizing |
| CN108715556A (en) * | 2018-08-17 | 2018-10-30 | 浙江小水滴环保科技有限公司 | Multifunctional ceramic material and its preparation method and application |
| CN109512261A (en) * | 2018-11-22 | 2019-03-26 | 宁波太尔炊具有限公司 | A kind of composite ceramics non-stick pan and preparation method thereof |
-
2019
- 2019-04-24 CN CN201910333470.2A patent/CN109896839B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7704754B2 (en) * | 2004-01-27 | 2010-04-27 | American Environmental Systems, Inc. | Method of plasmon-enhanced properties of materials and applications thereof |
| CN101744002A (en) * | 2009-12-29 | 2010-06-23 | 浙江理工大学 | Silicon-zinc mesoporous material silver-carrying antibacterial agent and preparation method thereof |
| CN104607039A (en) * | 2015-01-20 | 2015-05-13 | 济南木齐健康科技有限公司 | Composite material with anti-bacterial and purifying functions and preparation method of composite material |
| CN106348792A (en) * | 2016-08-26 | 2017-01-25 | 高名胜 | Manufacturing method of antibacterial ceramic tiles |
| CN107721369A (en) * | 2017-09-26 | 2018-02-23 | 苏州米颜生物科技有限公司 | It is a kind of non-burning brick with self-purification capacity with sterilizing |
| CN108715556A (en) * | 2018-08-17 | 2018-10-30 | 浙江小水滴环保科技有限公司 | Multifunctional ceramic material and its preparation method and application |
| CN109512261A (en) * | 2018-11-22 | 2019-03-26 | 宁波太尔炊具有限公司 | A kind of composite ceramics non-stick pan and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Thermodynamic assessments of the Ag–Tb and Ag–Ho systems;S.L.Wang et al.;《Journal of Alloys and Compounds》;20090918;第484卷(第1-2期);第102-107页 * |
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