CN113415995B - FFC ceramic, antibacterial easy-cleaning glaze thereof, preparation method and application - Google Patents
FFC ceramic, antibacterial easy-cleaning glaze thereof, preparation method and application Download PDFInfo
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- CN113415995B CN113415995B CN202110796148.0A CN202110796148A CN113415995B CN 113415995 B CN113415995 B CN 113415995B CN 202110796148 A CN202110796148 A CN 202110796148A CN 113415995 B CN113415995 B CN 113415995B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
Abstract
An FFC ceramic, an antibacterial easy-cleaning glaze thereof, a preparation method and an application thereof, wherein the antibacterial easy-cleaning glaze is prepared by mixing a base material, a high-boron low-temperature frit, a high-temperature frit and an antibacterial agent; the FFC ceramic is characterized in that the antibacterial easy-to-clean glaze cloth is applied to the surface of a blank body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the blank body after sintering; the preparation method comprises the steps of (1) to (3) to prepare the antibacterial easy-cleaning glaze. According to the scheme, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent are combined, so that the thermal expansion coefficient of the glaze is effectively balanced, the problem of cracking of the overglaze due to the fact that the expansion coefficients of the under glaze and the overglaze are not matched is solved, the components can form a layer of transparent glass body after being sintered, the smoothness degree of the whole glaze surface is increased, the stain adhesion probability is reduced, and the effect of easiness in cleaning is achieved; the problem of FFC glaze product when adding antibiotic easy clean overglaze, because the coefficient of expansion can't match easy glaze layer is cracked after firing the problem is solved, seriously influence product appearance and easy clean effect.
Description
Technical Field
The invention relates to the technical field of FFC (flexible flat cable) ceramics, in particular to FFC ceramics, an antibacterial easy-cleaning glaze thereof, a preparation method and application.
Background
And manufacturing a green body of the sanitary ceramic by using the FFC glaze. FFC is an abbreviation for Fine Fire Clay, a material used to make ceramics. The FFC glaze can be used for preparing a green body of sanitary ceramic through high-pressure grouting, but the sanitary ceramic green body prepared from the FFC glaze is easy to crack in a drying process or deform in a firing process, and most of the existing ceramic glaze contains low-temperature materials such as high-sodium stone powder, potassium-sodium feldspar and the like, so that the high-temperature resistance is low, and the green body is easy to deform at high temperature;
because the FFC product is limited by the combination of the green body, the ground glaze and the overglaze and the problem of matching of thermal expansion coefficients of the green body, the ground glaze and the overglaze, the formula structure of the overglaze cannot be easily adjusted; for example, when an antibacterial agent needs to be added on the FFC glaze or the formula needs to be changed to realize easy-cleaning effect, the problem of cracking of the glaze layer after sintering is easy to occur, and the appearance of the product is seriously influenced.
Disclosure of Invention
The invention aims to provide an antibacterial easy-cleaning glaze applied to FFC (flexible flat cable) ceramics, which is prepared by mixing a base material, a high-boron low-temperature frit, a high-temperature frit and an antibacterial agent.
The invention also provides the FFC ceramic, wherein the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
The invention also provides a preparation method of the antibacterial easy-to-clean glaze applied to the FFC ceramic, and the preparation method is used for preparing the antibacterial easy-to-clean glaze of the FFC ceramic.
The invention also provides an application of the antibacterial easy-to-clean glaze in the preparation of FFC (flexible flat cable) ceramics, wherein the antibacterial easy-to-clean glaze cloth is applied to the surface of a blank, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the blank after sintering.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antibacterial easy-cleaning glaze applied to FFC ceramics comprises the following raw materials in percentage by mass: 45-65% of base material, 3-16% of high-boron low-temperature frit, 25-40% of high-temperature frit and 5-13% of antibacterial agent;
the high-boron low-temperature frit comprises the following chemical components in percentage by mass: 64-70% of Si0 2 20 to 25% of B 2 O 3 5 to 7% of Na 2 O, 0-2% Al 2 O 3 0 to 1% of CaO, 0 to 1% of K 2 O, 0-1% of ZnO and 0-1% of BaO; the high-boron low-temperature frit has an expansion coefficient of (1.00-1.35) x 10 -7 The melting point of the high-boron low-temperature frit is 980-1100 ℃;
the high-temperature frit comprises the following chemical components in percentage by mass: 60-65% of Si0 2 4-9% of Al 2 O 3 4-12% CaO, 0-2% MgO, 1-7% K 2 O, 2-8% of ZnO and 0-5% of B 2 O 3 And 3-7% of BaO; the expansion coefficient of the high-temperature frit is (1.85-1.98) multiplied by 10 -7 /° c; the melting point of the high-temperature frit is 1200-1250 ℃.
Preferably, the antibacterial agent comprises the following components in percentage by mass: the nano zinc oxide accounts for 6-12% of the total mass of the raw materials, and the nano silver ion antibacterial agent accounts for 0.01-1% of the total mass of the raw materials.
Preferably, the base stock comprises the following raw materials: potassium feldspar, quartz powder, wollastonite, alumina and calcined talcum powder;
the antibacterial easy-cleaning glaze comprises the following raw materials in percentage by mass: 10-22% of potassium feldspar, 13-20% of quartz powder, 8-15% of wollastonite, 3-8% of alumina, 7-13% of sintered talcum powder, 3-16% of high-boron low-temperature frit, 25-40% of high-temperature frit and 5-13% of an antibacterial agent.
Preferably, the raw materials further comprise: a pigment for dyeing the antibacterial easy-cleaning glaze.
Preferably, the raw materials are ball-milled until 10 mu m is more than or equal to 80 percent and D50 is less than or equal to 3.0 mu m.
An FFC ceramic comprising: a blank and the antibacterial easy-cleaning glaze applied to the FFC ceramic;
the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
Preferably, the thickness of the antibacterial easy-cleaning glaze on the blank body is 0.05-0.1 mm.
A preparation method of an antibacterial easy-to-clean glaze applied to FFC ceramics is used for preparing the antibacterial easy-to-clean glaze applied to the FFC ceramics, and comprises the following steps:
step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent in proportion to form a primary material;
step (2): and (2) performing ball milling on the primary material in the step (1) until the particle size of 10 microns is more than or equal to 80 percent and the particle size of D50 is less than or equal to 3.0 microns to prepare the antibacterial easy-to-clean glaze.
Preferably, the method further comprises the following steps: step (3);
the step (3): adding pigment before or after ball milling of the antibacterial easy-cleaning glaze.
The application of the antibacterial easy-to-clean glaze in the preparation of the FFC ceramic uses the antibacterial easy-to-clean glaze applied to the FFC ceramic;
the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
The technical scheme provided by the invention can have the following beneficial effects:
according to the scheme, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent are combined, so that the thermal expansion coefficient of the glaze is effectively balanced, the problem of cracking of the overglaze due to the fact that the expansion coefficients of the under glaze and the overglaze are not matched is solved, meanwhile, the components form a layer of transparent glass body on the basis of the original glaze layer after being sintered, the smoothness degree of the whole glaze layer is increased, the stain adhesion probability is reduced, and the easy-cleaning effect is achieved; the problem of FFC glaze product when adding antibiotic easy clean overglaze, because the coefficient of expansion can't match easy glaze layer is cracked after firing the problem is solved, seriously influence product appearance and easy clean effect.
Detailed Description
The technical solution of the present solution is further explained by the following specific embodiments.
An antibacterial easy-cleaning glaze applied to FFC ceramics comprises the following raw materials in percentage by mass: 45-65% of base material, 3-16% of high-boron low-temperature frit, 25-40% of high-temperature frit and 5-13% of antibacterial agent;
the high-boron low-temperature frit comprises the following chemical components in percentage by mass: 64-70% of Si0 2 20 to 25% of B 2 O 3 5 to 7% of Na 2 O, 0-2% Al 2 O 3 0 to 1% of CaO, 0 to 1% of K 2 O, 0-1% of ZnO and 0-1% of BaO; the high-boron low-temperature frit has an expansion coefficient of (1.00-1.35) x 10 -7 The melting point of the high-boron low-temperature frit is 980-1100 ℃;
the high-temperature frit comprises the following chemical components in percentage by mass: 60-65% of Si0 2 4-9% of Al 2 O 3 4-12% CaO, 0-2% MgO, 1-7% K 2 O, 2-8% of ZnO and 0-5% of B 2 O 3 And 3-7% of BaO; the expansion coefficient of the high-temperature frit is (1.85-1.98) multiplied by 10 -7 /° c; the melting point of the high-temperature frit is 1200-1250 ℃.
According to the scheme, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent are combined, so that the thermal expansion coefficient of the glaze is effectively balanced, the problem of cracking of the overglaze due to the fact that the expansion coefficients of the under glaze and the overglaze are not matched is solved, meanwhile, the components form a layer of transparent glass body on the basis of the original glaze layer after being sintered, the smoothness degree of the whole glaze layer is increased, the stain adhesion probability is reduced, and the easy-cleaning effect is achieved; the problem of FFC glaze product when adding antibiotic easy clean overglaze, because the coefficient of expansion can't match easy glaze layer is cracked after firing the problem is solved, seriously influence product appearance and easy clean effect.
In particular, the base material is replaced by a component of a known overglaze, for example SiO as chemical component 2 、Al 2 O 3 、K 2 O、Na 2 O, CaO, MgO, BaO, ZnO, etc.; raw material components such as quartz, potassium feldspar, albite, calcite, calcined talc, dolomite and the like; when the base material is in the range of 45-65%, the base material provided by the base material has better effect, and the overglaze has good glass effect and texture.
High boron low temperature frit, which is B-rich 2 O 3 After the glaze is mixed with the high-temperature frit, on one hand, the thermal expansion coefficient of the glaze can be balanced, the cracking of the overglaze caused by the mismatching of the expansion coefficients of the ground glaze, the blank and the overglaze is reduced, and a layer of transparent glass body can be formed on the basis of the original glaze layer after the glaze is sintered, so that the smoothness of the whole glaze layer is increased, the stain adhesion probability is reduced, and the effect of easy cleaning is achieved. The overglaze of the scheme can be tested for many times in a circulating way under the temperature difference of 0-140 ℃, the cracking problem of a glaze layer does not exist, and the smoothness degree can reach that the glaze surface painted by the ink pen can be easily washed clean only by small water flow.
The antibacterial agent is replaced by a component with the known antibacterial function, such as nano gold, nano silver, zinc oxide and the like, and is used for providing the antibacterial function for the glaze.
Preferably, the antibacterial agent comprises the following components in percentage by mass: the nano zinc oxide accounts for 6-12% of the total mass of the raw materials, and the nano silver ion antibacterial agent accounts for 0.01-1% of the total mass of the raw materials.
According to the scheme, the nano zinc oxide and the nano silver ion antibacterial agent are preferably used in a matched mode, the antibacterial effect is the best embodiment of the combination of the antibacterial agents, and based on the scheme, the nano silver ion antibacterial agent with the content of 0.01-1% can be added to achieve the excellent antibacterial effect, so that the cost is low; preferably, 0.01 to 0.5%, more preferably 0.01 to 0.1%, and most preferably 0.01 to 0.07% is used.
Preferably, the base stock comprises the following raw materials: potassium feldspar, quartz powder, wollastonite, alumina and calcined talcum powder;
the antibacterial easy-cleaning glaze comprises the following raw materials in percentage by mass: 10-22% of potassium feldspar, 13-20% of quartz powder, 8-15% of wollastonite, 3-8% of alumina, 7-13% of calcined talcum powder, 3-16% of high-boron low-temperature frit, 25-40% of high-temperature frit and 5-13% of an antibacterial agent.
The base material can be oxide or other metal compound conventionally selected by known glaze, potassium feldspar, quartz powder, wollastonite, alumina and calcined talcum powder are preferably used in the scheme, and the snowflake-shaped grains prepared according to the scheme have the advantages of stable effect, no over-obvious effect, no over-light effect and excellent smoothness.
More preferably, the raw materials further comprise: a pigment for dyeing the antibacterial easy-cleaning glaze.
The colorant of the scheme can be replaced by a colorant with a known dyeing effect, is only used for decoration, and cannot influence the performance of glaze materials, such as synthetic pigments, inorganic pigments (iron oxide, carbon black, chromium oxide green and the like), natural pigments (bixin, cochineal, chlorophyll, curcumin, phyllanthin and the like); the scheme preferably uses edible pigments, such as pigments directly extracted from animal and plant tissues, red yeast rice, chlorophyll, curcumin, carotene, amaranth, sugar color and the like, and can display red, green, yellow, bright blue, purple and the like, so that the overglaze and the lower glaze have different colors. When the scheme uses the edible pigment, the scheme is provided with the antibacterial agent, so that the pigment is kept stable in the antibacterial easy-cleaning glaze and is not easy to fade.
Preferably, the raw materials are ball-milled until 10 mu m is more than or equal to 80 percent and D50 is less than or equal to 3.0 mu m. The content of particles having a particle size of 10 μm or more and 80% or less means that the particle size is 80% or less than 10 μm, and the content of particles having a particle size of 50% or less and D50 or less is 3.0 μm or less.
The overglaze with the formula can reduce large-particle substances in the overglaze by controlling the particle size distribution so as to achieve the effect of inhibiting overglaze crystallization and prevent the overglaze from generating crystallization matte phenomenon under the condition of low-temperature quick-firing of re-firing in order to improve the transparency of an overglaze layer.
An FFC ceramic comprising: the green body and the antibacterial easy-cleaning glaze applied to the FFC ceramic in any embodiment;
the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
FFC ceramic, FFC is an abbreviation for Fine Fire Clay, a material used to make ceramics. The FFC glaze slurry can be used for preparing a green body of sanitary ceramic through high-pressure grouting, the green body of the sanitary ceramic prepared from the FFC glaze slurry is easy to crack in a drying process or deform in a firing process, and most of the conventional ceramic glaze materials contain low-temperature materials such as high-sodium stone powder, potassium-sodium feldspar and the like, so that the high-temperature resistance is low, the green body is easy to deform at high temperature, and the glaze layer on the surface of the sanitary ceramic has glaze defects such as tiny pinholes, unevenness, microcracks and the like which cannot be seen by naked eyes.
According to the scheme, the antibacterial easy-to-clean glaze cloth is applied to the surface of a blank of the FFC ceramic, so that the cracking problem of the surface glaze of the FFC is solved, the smoothness of the whole glaze surface is improved, the stain attachment probability is reduced, the easy-to-clean effect is achieved, and meanwhile, the antibacterial agent provides antibacterial capability for the FFC ceramic; in addition, the scheme can form a light snowflake-shaped grain effect on the overglaze on the surface of the blank body so as to endow the glaze with unique and easy-to-clean property.
Preferably, the thickness of the antibacterial easy-cleaning glaze on the blank body is 0.05-0.1 mm.
In some embodiments, the thickness of the antibacterial easy-cleaning glaze can be in a range of 0.05-0.1 mm; in the scheme, the thickness of the antibacterial easy-cleaning glaze is preferably controlled to be 0.05-0.1mm, the performances in all aspects are optimal, and in some embodiments, the glaze layer after sintering cannot completely cover the ground glaze due to the fact that the overglaze is too thin, so that the easy-cleaning performance is greatly influenced; in some embodiments, the overglaze is too thick, so that snowflake-shaped lines in the glaze layer are too obvious, and the appearance of the glaze layer is also influenced.
A preparation method of the antibacterial easy-cleaning glaze applied to the FFC ceramic, which is used for preparing the antibacterial easy-cleaning glaze applied to the FFC ceramic in any one of claims 1 to 4, and comprises the following steps:
step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent in proportion to form a primary material;
step (2): and (2) performing ball milling on the primary material in the step (1) until the particle size of 10 microns is more than or equal to 80 percent and the particle size of D50 is less than or equal to 3.0 microns to prepare the antibacterial easy-to-clean glaze.
Preferably, the method further comprises the following steps: step (3);
the step (3): adding pigment before or after ball milling of the antibacterial easy-cleaning glaze.
The application of the antibacterial easy-to-clean glaze in the preparation of the FFC ceramic uses the antibacterial easy-to-clean glaze applied to the FFC ceramic;
the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
And (3) performance testing:
easy cleaning performance:
the easy-to-clean property of the FFC ceramic is tested according to GB/T31859 & 2015 daily-use porcelain easy-to-clean property detection method. And (3) representing the residual amount of the oil stain in unit area by adopting A:
A≤0.50g/m 2 easy to clean; 0.50g/m 2 ＜A≤1.00g/m 2 In order to facilitate the cleaning of the cleaning tool,
1.00g/m 2 ＜A≤1.5g/m 2 is cleanable; a > 1.5g/m 2 It is not cleanable.
Antibacterial property:
the antibacterial property of the FFC ceramic is tested according to JC/T897-2014 antibacterial ceramic antibacterial property, wherein Escherichia coli AS1.90 and staphylococcus aureus AS1.89 are mainly used.
Anti-cracking performance:
and (3) heating the FFC ceramic at the speed of 10 ℃/h in the environment of 20 ℃ until the temperature reaches 160 ℃, then quenching the FFC ceramic to 20 ℃, repeating the steps for 3 times, and observing whether the FFC ceramic cracks.
Example A:
the high boron low temperature frit used in example a had a chemical composition comprising, in mass percent, 65% Si0 2 25% of B 2 O 3 5% of Na 2 O, 1% of Al 2 O 3 1% of CaO, 1% of K 2 O, 1% ZnO and 1% BaO; the high boron low temperature frit has an expansion coefficient of 1.25 x 10 -7 V, the melting point of the high-boron low-temperature frit is 1000 ℃;
the high boron low temperature frit used in example a comprises the following chemical components in percentage by mass: 65% Si0 2 9% of Al 2 O 3 4% of CaO, 7% of K 2 O, 8% ZnO and 7% BaO; the high-temperature frit has an expansion coefficient of 1.90 × 10 -7 /° c; the melting point of the high-temperature frit is 1230 ℃.
The sanitary ware of example a was prepared by the method:
step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent in proportion to form a primary material according to the table 1;
step (2): and (2) performing ball milling on the primary material in the step (1) until the particle size of 10 microns is more than or equal to 80 percent and the particle size of D50 is less than or equal to 3.0 microns to prepare the antibacterial easy-to-clean glaze.
And (3): the antibacterial easy-cleaning glaze cloth is applied to the surface of the sanitary ceramic blank made of the FFC material and sintered at 1300 ℃, and a cover glaze layer is formed on the surface of the sanitary ceramic blank with the ground glaze, wherein the thickness of the antibacterial easy-cleaning glaze on the blank is 0.1 mm.
TABLE 1 compositions of example A
| Raw materials | Example A1 | Example A2 | Example A3 | Comparative example A1 | Comparative example A2 |
| Potassium feldspar (%) | 10 | 22 | 16 | 15 | 22 |
| Quartz powder (%) | 20 | 13 | 17 | 20 | 20 |
| Wollastonite (%) | 8 | 8 | 8 | 13 | 15 |
| Alumina (%) | 8 | 3 | 5 | 8 | 8 |
| Burned talc (%) | 7 | 13 | 7 | 13 | 13 |
| High boron low temperature frit (%) | 16 | 3 | 8 | 0 | 16 |
| High temperature frit (%) | 25 | 32 | 25 | 25 | 0 |
| Nano zinc oxide (%) | 5.9 | 5.9 | 13 | 5.9 | 5.9 |
| Nano silver ion (%) | 0.1 | 0.1 | 1 | 0.1 | 0.1 |
The above examples were subjected to performance tests to obtain Table 2.
TABLE 2 Performance testing of example A
Description of the invention:
1. as can be seen from comparison of comparative example a1, comparative example a2, and example a1, comparative example a1 has no added high boron low temperature frit, and actually carries only high temperature frit; comparative example a2 with no high temperature frit added, actually only with high boron low temperature frit; however, when the glazes of the comparative example A1 and the comparative example A2 act on the FFC ceramic blank, the FFC ceramic blank is sintered, and the expansion coefficients of the ground glaze, the blank and the cover glaze cannot be matched, so that the FFC ceramic has a cracking phenomenon in the temperature difference adjusting process of being close to 140 ℃;
2. the glazes of comparative example a1 and comparative example a2, which used a single high boron low temperature frit or high temperature frit, did not combine the high boron low temperature frit with the high temperature frit after firing to form a transparent glass layer having easy-to-clean effect, comparative example a1 and comparative example a2 did not have good self-cleaning effect, except that comparative example a1 had an a value of 1.45g/m 2 Is cleanable, in cleaningThe stains need to be rubbed for a plurality of times; comparative example A2 had an A value of 1.67g/m 2 The stains are not cleanable and remain after being rubbed for many times.
3. The frit formulations of comparative examples a1 and a2 formulated with an antibacterial agent using a single high boron low temperature frit or high temperature frit are not suitable for FFC ceramics and, in addition to the above-described cracking phenomenon, the antibacterial effect is reduced.
4. The examples A1-A3 all used high-boron low-temperature frit high-temperature frit and antibacterial agent at the same time, when compared with the comparative examples A1-A2, when any component in the formula of examples A1-A3 is adjusted within a certain range, especially the percentage adjustment of nano zinc oxide and nano silver ions does not affect the easy-cleaning performance, antibacterial performance and anti-cracking performance of the FFC ceramic, and the stability of the FFC ceramic is ensured.
Example B:
the high boron low temperature frit used in example B had a chemical composition comprising, by mass%, 70% Si0 2 20% of B 2 O 3 7% of Na 2 O, 1% of K 2 O, 1% ZnO and 1% BaO; the high boron low temperature frit has an expansion coefficient of 1.30 x 10 -7 The melting point of the high-boron low-temperature frit is 980 ℃;
the high boron low temperature frit used in example B comprises, in mass percent, the chemical composition: 60% Si0 2 4% of Al 2 O 3 12% of CaO, 7% of K 2 O, 1% MgO, 8% ZnO, 5% B 2 O 3 And 3% BaO; the high-temperature frit has an expansion coefficient of 1.91 x 10 -7 /° c; the melting point of the high-temperature frit is 1250 ℃.
The sanitary ware of example B was prepared by the method:
step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent into a primary material according to the proportion in the table 3;
step (2): and (2) performing ball milling on the primary material in the step (1) until the particle size of 10 microns is more than or equal to 80 percent and the particle size of D50 is less than or equal to 3.0 microns to prepare the antibacterial easy-to-clean glaze.
And (3): the antibacterial easy-cleaning glaze cloth is applied to the surface of the sanitary ceramic blank made of the FFC material and sintered at 1310 ℃, and a cover glaze layer is formed on the surface of the sanitary ceramic blank with the ground glaze, wherein the thickness of the antibacterial easy-cleaning glaze on the blank is 0.1 mm.
TABLE 3 compositions of example B
| Components | Example B1 | Example B2 | Example B3 | Example B4 | Example B5 |
| Potassium feldspar (%) | 19 | 18 | 17 | 10 | 10 |
| Quartz powder (%) | 19 | 20 | 20 | 20 | 18 |
| Wollastonite (%) | 13 | 13 | 8 | 8 | 8 |
| Alumina (%) | 8 | 8 | 8 | 8 | 8 |
| Burned talc (%) | 9 | 7 | 7 | 7 | 7 |
| High boron low temperature frit (%) | 1 | 3 | 9 | 16 | 18 |
| High temperature frit (%) | 25 | 25 | 25 | 25 | 25 |
| Nano zinc oxide (%)) | 5.9 | 5.9 | 5.9 | 5.9 | 5.9 |
| Nano silver ion (%) | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
The above examples were subjected to performance tests to obtain Table 4.
TABLE 4 Performance testing of example B
Description of the drawings:
the addition amount of the high-boron low-temperature frit cannot be too high or too low; as shown by comparison between example B1 and example B5, the addition amount of the high boron low temperature frit of example B1 is 1%, which is 2% less than the 3% addition amount of example B2, and the addition amount is too small, so that the prepared FFC ceramic can not resist the temperature difference change of 0-140 ℃, and the easy-to-clean performance and the antibacterial performance are insufficient compared with example B2; whereas the high boron low temperature frit of example B5 was added at 18% more than the 16% addition of example B4 by 2%, although the FFC ceramic of example B5 withstood temperature differential changes from 0-140 ℃ without cracking, its surface had decreased cleanability, was not easily removed when smudges occurred, and had decreased overglaze transparency.
In the embodiment B2-the embodiment B4, the addition amount of the high-boron low-temperature frit is controlled to be 3-16%, and the easy-cleaning performance, the antibacterial performance and the anti-cracking performance of the FFC ceramic are optimal according to the addition amount range; the FFC ceramic is stable and does not crack when the addition amount of the high-boron low-temperature frit is controlled to be 3-16%, and has the best performance.
Example C
The high boron low temperature frit used in example C had a chemical composition comprising, by weight percent, 70% Si0 2 20% of B 2 O 3 7% of Na 2 O, 1% of K 2 O, 1% ZnO and 1% BaO; the high boron low temperature frit has an expansion coefficient of 1.30 x 10 -7 The melting point of the high-boron low-temperature frit is 980 ℃;
the high boron low temperature frit used in example C comprises, in mass percent, the chemical composition: 60% Si0 2 4% of Al 2 O 3 12% of CaO, 7% of K 2 O, 1% MgO, 8% ZnO, 5% B 2 O 3 And 3% BaO; the high-temperature frit has an expansion coefficient of 1.91 x 10 -7 /° c; the melting point of the high-temperature frit is 1250 ℃.
Preparation of the sanitary ceramic of example C:
step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent in proportion to form a primary material according to the table 5;
step (2): and (2) performing ball milling on the primary material in the step (1) until the particle size of 10 microns is more than or equal to 80 percent and the particle size of D50 is less than or equal to 3.0 microns to prepare the antibacterial easy-to-clean glaze.
And (3): the antibacterial easy-cleaning glaze cloth is applied to the surface of the sanitary ceramic blank made of the FFC material and sintered at 1310 ℃ to form a cover glaze layer on the surface of the sanitary ceramic blank with the ground glaze, and the thickness of the antibacterial easy-cleaning glaze on the blank is 0.1 mm.
TABLE 5 ingredients of example C
The above examples were subjected to performance tests to obtain Table 6.
TABLE 6 Performance testing of example C
Description of the drawings:
the high-temperature frit cannot be too low or too high, the high-temperature frit and the high-boron low-temperature frit cannot form a layer of transparent glass body with an easy-to-clean function due to the too low temperature frit, and the antibacterial effect of the antibacterial agent is reduced due to the too high temperature frit; as in example C1, the high temperature frit of example C1 was added at 20% level, while the FFC ceramic of example C1 had an easy clean A value of 1.51g/m 2 (ii) a The addition amount of the high-temperature frit in the example C2 is 25%, which is 5% more than that in the example C1, the FFC ceramic in the example C2 is easy to clean, and the FFC ceramic in the example C1 is not easy to clean; meanwhile, when the content of the high-temperature frit reaches 25% of that of the embodiment C2, the content of the high-temperature frit is continuously increased to 30% of that of the embodiment C3, 35% of that of the embodiment C4 and 40% of that of the embodiment C5, and the embodiments C2-C5 have better easy-cleaning performance, antibacterial performance and anti-cracking performance; however, when the content of the high-temperature frit of example C5 was further increased from 40% to 45% of example C6, the easy-cleaning property began to be decreased, and the antibacterial property was decreased, and the power against escherichia coli was only 78.62% and the power against staphylococcus aureus was only 77.77%.
Therefore, although the high-temperature frit can be used in combination with the high-boron low-temperature frit, the addition range of the high-temperature frit is within 25-40% to ensure that the high-temperature frit is matched with the base material, the high-boron low-temperature frit and the antibacterial agent in the formula, so that the transparent glass body generated on the surface of the FFC ceramic has stability, the overglaze layer has an easy-cleaning effect at the same time, the antibacterial agent can normally express an antibacterial effect, and the anti-cracking effect of the FFC body is effectively matched with the antibacterial easy-cleaning glaze.
Example D:
based on the step (1) and the step (2) of the example C4, in the step (3), the antibacterial easy-to-clean glaze was applied to the surface of the FFC sanitary ceramic body, and sintered at 1310 ℃ to form a cover glaze layer on the surface of the sanitary ceramic body with the ground glaze, and the thickness of the antibacterial easy-to-clean glaze in the body was as shown in table 7.
TABLE 7 Performance testing of example D
Description of the drawings:
the scheme preferably limits the thickness of the antibacterial easy-cleaning glaze to 0.05-0.1mm, and in the range, the easy-cleaning performance of the FFC ceramic is optimal and easy to clean; but when the thickness of the antibacterial easy-cleaning glaze is too thin or too thick, the easy-cleaning performance is reduced; for example, examples D1 and D6, examples D1 and D6 are easier to clean, but the combination of antimicrobial and crack resistance is still superior.
Example E:
the high boron low temperature frit used in example E had a chemical composition comprising, by mass percent, 64% Si0 2 25% of B 2 O 3 6% of Na 2 O, 2% of Al 2 O 3 0.5 percent of CaO, 0.5 percent of K 2 O, 1% ZnO and 1% BaO; the high boron low temperature frit has an expansion coefficient of 1.26 x 10 -7 /° c, the melting point of the high-boron low-temperature frit is 1010 ℃;
the high boron low temperature frit used in example E comprises, in mass percent, the chemical composition: 63% Si0 2 7% of Al 2 O 3 8% of CaO, 2% of MgO and 3% of K 2 O, 5% ZnO, 5% B 2 O 3 And 7% BaO; the high-temperature frit has an expansion coefficient of 1.93 x 10 -7 /° c; the melting point of the high-temperature frit is 1240 ℃.
The antibacterial easy-cleaning glaze comprises the following raw materials in percentage by mass: 13% of potassium feldspar, 15% of quartz powder, 9% of wollastonite, 4% of alumina, 9% of calcined talcum powder, 9% of high-boron low-temperature frit, 35% of high-temperature frit, 5.95% of nano zinc oxide and 0.05% of nano silver ions.
Example F:
high boron low temperature frit used in example F, by massPercent, chemical composition including 66% Si0 2 23% of B 2 O 3 6% of Na 2 O, 2% of Al 2 O 3 0.5 percent of CaO, 0.5 percent of K 2 O, 1% ZnO and 1% BaO; the expansion coefficient of the high-boron low-temperature frit is 1.26 multiplied by 10 -7 /° c, the melting point of the high-boron low-temperature frit is 1010 ℃;
the high boron low temperature frit used in example F comprises, in mass percent, the chemical composition: 63% Si0 2 7% of Al 2 O 3 8% of CaO, 2% of MgO and 3% of K 2 O, 5% ZnO, 5% B 2 O 3 And 7% BaO; the high-temperature frit has an expansion coefficient of 1.93 x 10 -7 /° c; the melting point of the high-temperature frit is 1240 ℃.
The antibacterial easy-cleaning glaze comprises the following raw materials in percentage by mass: 13% quartz, 13% albite, 6% calcite, 6% talc, 20% dolomite, 9% high boron low temperature frit, 27% high temperature frit, 5.95% nano zinc oxide and 0.05% nano silver ions.
Example G:
the high boron low temperature frit used in example G had a chemical composition comprising, in mass percent, 66% Si0 2 23% of B 2 O 3 6% of Na 2 O, 2% of Al 2 O 3 0.5 percent of CaO and 0.5 percent of K 2 O, 1% ZnO and 1% BaO; the high boron low temperature frit has an expansion coefficient of 1.26 x 10 -7 /° c, the melting point of the high-boron low-temperature frit is 1010 ℃;
the high boron low temperature frit used in example G comprises the following chemical components in percentage by mass: 63% Si0 2 7% of Al 2 O 3 8% of CaO, 2% of MgO and 3% of K 2 O, 5% ZnO, 5% B 2 O 3 And 7% BaO; the high-temperature frit has an expansion coefficient of 1.93 x 10 -7 /° c; the melting point of the high-temperature frit is 1240 ℃.
The antibacterial easy-cleaning glaze comprises the following raw materials in percentage by mass: 25.9% quartz, 6% albite, 11% calcite, 3% kaolin, 18% dolomite, 9% high boron low temperature frit, 27% high temperature frit and 0.1% nanogold.
Step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent in proportion to form a primary material according to the above examples E to G;
step (2): performing ball milling on the primary material in the step (1) until the particle size distribution of the transparent frits in the glaze is as follows: 0-0.5% of 60-mesh screen residue, 40-80% of 250-mesh screen residue and 325-mesh screen residue: 80-99.5% of the antibacterial easy-cleaning glaze, and 0.1% of carotene in the total mass is added as an edible pigment;
and (3): the antibacterial easy-cleaning glaze cloth is applied to the surface of the sanitary ceramic blank made of the FFC material and sintered at 1310 ℃ to form a cover glaze layer on the surface of the sanitary ceramic blank with the ground glaze, and the thickness of the antibacterial easy-cleaning glaze on the blank is 0.05 mm.
The FFC ceramics from examples E to G were tested for performance as shown in Table 8.
Performance testing of examples E-G
The technical principle of the present solution is described above with reference to specific embodiments. These descriptions are only used to explain the principles of the present solution and should not be interpreted in any way as limiting the scope of the present solution. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present solution without any inventive effort, which would fall within the scope of the present solution.
Claims (9)
1. The application of the antibacterial easy-to-clean glaze in the preparation of FFC (flexible flat cable) ceramics is characterized in that the antibacterial easy-to-clean glaze comprises the following raw materials in percentage by mass: 45-65% of base material, 3-16% of high-boron low-temperature frit, 25-40% of high-temperature frit and 5-13% of antibacterial agent;
the high-boron low-temperature frit comprises the following chemical components in percentage by mass: 64-70% of Si0 2 、2025% of B 2 O 3 5 to 7% of Na 2 O, 0-2% Al 2 O 3 0 to 1% of CaO, 0 to 1% of K 2 O, 0-1% of ZnO and 0-1% of BaO; the high-boron low-temperature frit has an expansion coefficient of (1.00-1.35) x 10 -7 The melting point of the high-boron low-temperature frit is 980-1100 ℃;
the high-temperature frit comprises the following chemical components in percentage by mass: 60-65% of Si0 2 4-9% of Al 2 O 3 4-12% CaO, 0-2% MgO, 1-7% K 2 O, 2-8% of ZnO and 0-5% of B 2 O 3 And 3-7% of BaO; the expansion coefficient of the high-temperature frit is (1.85-1.98) multiplied by 10 -7 /° c; the melting point of the high-temperature frit is 1200-1250 ℃;
the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
2. The use of the antibacterial easy-clean glaze according to claim 1 in the preparation of FFC ceramics, wherein the antibacterial agent comprises the following components in percentage by mass: the nano zinc oxide accounts for 6-12% of the total mass of the raw materials, and the nano silver ion antibacterial agent accounts for 0.01-1% of the total mass of the raw materials.
3. The use of the antibacterial easy-clean glaze according to claim 1 or 2 in the preparation of FFC ceramics, wherein the raw materials further comprise: a pigment for dyeing the antibacterial easy-cleaning glaze.
4. The use of the antibacterial easy-clean glaze according to claim 1 or 2 in the preparation of FFC ceramics, wherein the base stock comprises the following raw materials: potassium feldspar, quartz powder, wollastonite, alumina and calcined talcum powder;
the antibacterial easy-cleaning glaze comprises the following raw materials in percentage by mass: 10-22% of potassium feldspar, 13-20% of quartz powder, 8-15% of wollastonite, 3-8% of alumina, 7-13% of calcined talcum powder, 3-16% of high-boron low-temperature frit, 25-40% of high-temperature frit and 5-13% of an antibacterial agent.
5. The use of the antibacterial easy-cleaning glaze in the preparation of FFC ceramics according to claim 1 or 2, wherein the raw materials are ball-milled to 10 μm or more and 80% or less, and D50 or less and 3.0 μm or less.
6. An FFC ceramic, comprising: an antibacterial easy-to-clean glaze for manufacturing FFC ceramics, the green body and the use of the antibacterial easy-to-clean glaze according to any one of claims 1 to 5;
the antibacterial easy-to-clean glaze cloth is applied to the surface of the green body, and a cover glaze layer with an antibacterial easy-to-clean effect is formed on the surface of the green body after sintering.
7. The FFC ceramic of claim 6, wherein the thickness of the antibacterial easy-clean glaze on the green body is 0.05-0.1 mm.
8. A method for preparing an antibacterial easy-to-clean glaze applied to an FFC ceramic, wherein the antibacterial easy-to-clean glaze for preparing the use of the antibacterial easy-to-clean glaze of any one of claims 1 to 5 in the preparation of the FFC ceramic comprises the following steps:
step (1): mixing the base material, the high-boron low-temperature frit, the high-temperature frit and the antibacterial agent in proportion to form a primary material;
step (2): and (2) performing ball milling on the primary material in the step (1) until the ball milling is carried out until the 10 mu m is more than or equal to 80 percent and the D50 is less than or equal to 3.0 mu m, thus obtaining the antibacterial easy-cleaning glaze.
9. The method for preparing the antibacterial easy-to-clean glaze applied to the FFC ceramic according to claim 8, further comprising the following steps: step (3);
the step (3): adding pigment before or after ball milling of the antibacterial easy-cleaning glaze.
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