CN113929497B - Antibacterial and antiskid ceramic tile and preparation method thereof - Google Patents
Antibacterial and antiskid ceramic tile and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial and antiskid ceramic tile and a preparation method thereof. The preparation method of the antibacterial and anti-skid ceramic tile comprises the following steps: applying anti-slip glaze on the surface of the green brick, wherein the mineral composition of the anti-slip glaze is corundum; sintering the green brick after the anti-slip glaze is applied in the first stage; the highest temperature of the first stage sintering is 1200 to 1220 ℃, and the sintering period is 50 to 60min; after the first-stage firing is completed, applying antibacterial glaze on the surface of the adobe with the anti-slip glaze and performing second-stage firing to melt the antibacterial glaze and firmly combine and fix the antibacterial glaze and the anti-slip glaze on the surface of the adobe to obtain the antibacterial anti-slip ceramic tile; the maximum temperature of the second stage sintering is 650 to 750 ℃, and the sintering period is 5 to 10min.
Description
Technical Field
The invention relates to an antibacterial antiskid ceramic tile and a preparation method thereof, belonging to the technical field of ceramic tile production and manufacturing.
Background
At present, the grade of architectural decoration in China is continuously improved, and a large number of public buildings such as floors of hotels, office buildings, shopping buildings, high-grade apartments and the like adopt a large number of elegant stone plates, glazed tiles and the like, so that the environment is beautified, and meanwhile, the problem of increasingly prominent potential safety hazard of floor slip is also brought. At present, accidents such as accidental slipping, injury and disability are increased due to the fact that the ground is too smooth in domestic public places, and ground skid resistance becomes a new problem of public safety. Meanwhile, in these public places, bacteria are easily bred in humid environments, food residues, spray and the like, and if the bacteria cannot be cleaned in time, a large amount of bacteria pollution can be caused, so that the health of people is harmed. Therefore, the ceramic tile product with the antibacterial and anti-skid functions is developed, has higher practical value, and can reduce the risk of slipping and infecting bacteria. At present, some ceramic enterprises put out ceramic tiles with anti-skid function, and the ceramic tiles add relatively thick corundum into protective glaze or use high-temperature dry particles to realize anti-skid. However, in order to avoid the corundum from being reacted due to the excessively small fineness, the corundum needs to be large enough to generate protrusions on the outer layer of the protective glaze so as to have the anti-slip effect, but the protrusions exposed on the outer layer of the protective glaze easily cause rough hand feeling and blocking dirt. Some ceramic manufacturing enterprises also put ceramic tiles with antibacterial function, for example, negative ion powder is added for sterilization, but the negative ion powder is mainly excited by radioactive elements, so that ceramic products have certain radioactivity; for example, the photocatalytic mechanism sterilization is mainly performed by coating nano titanium dioxide on the surface of a product, but because the antibacterial action of the nano titanium dioxide needs to be excited by ultraviolet rays, the product needs to be treated at low temperature of about 300 ℃ frequently to keep the antibacterial activity, in addition, the antibacterial durability of the ceramic product needs to be improved, and the ultraviolet rays are harmful to human bodies; for example, an antibacterial agent such as silver is added to glaze and directly fired, but the high-temperature environment easily causes silver to be oxidized, thereby reducing antibacterial ability.
Disclosure of Invention
Aiming at the problems, the invention provides an antibacterial anti-slip ceramic tile and a preparation method thereof, which realize the combination of antibacterial and anti-slip functions of the ceramic tile by simultaneously using the anti-slip glaze and the antibacterial glaze and adjusting the preparation process, and the antibacterial anti-slip ceramic tile has the advantages of not rough hand feeling, high anti-slip performance, excellent antibacterial function and no toxicity or harm to human bodies and environment.
In a first aspect, the invention provides a preparation method of an antibacterial and antiskid ceramic tile, which comprises the following steps:
applying anti-slip glaze on the surface of the green brick, wherein the mineral composition of the anti-slip glaze is corundum;
sintering the green brick after the anti-slip glaze is applied in the first stage; the highest temperature of the first stage sintering is 1200-1220 ℃, and the sintering period is 50-60 min;
after the first-stage firing is completed, applying antibacterial glaze on the surface of the adobe with the anti-slip glaze and performing second-stage firing to melt the antibacterial glaze and firmly combine and fix the antibacterial glaze and the anti-slip glaze on the surface of the adobe to obtain the antibacterial anti-slip ceramic tile; the maximum temperature of the second stage sintering is 650-750 ℃, and the sintering period is 5-10 min.
Preferably, the application mode of the anti-slip glaze is glaze spraying, and the specific gravity of the anti-slip glaze is 1.10-1.15 g/cm 3 The glazing amount is 60-80 g/m 2 。
Preferably, the chemical composition of the antibacterial glaze comprises: by mass percent, siO 2 ：21～26％、Al 2 O 3 ：1.0～1.5％、CaO：18～21％、MgO：0.2～0.3％、K 2 O：0.2～0.3％、Na 2 O：6～8％、B 2 O 3 ：15～19％、P 2 O 5 ：4～6％、Ag：0.20～0.30％、ZnO：6～8％、ZrO 2 : 5-7%, loss on ignition: 8.8 to 12 percent.
Preferably, the application mode of the antibacterial glaze is glaze spraying, and the specific gravity of the antibacterial glaze is 1.05-1.10 g/cm 3 The glazing amount is 70 to 90g/m 2 。
Preferably, the melting starting temperature of the antibacterial glaze is 500-550 ℃.
Preferably, the raw material composition of the antibacterial glaze comprises: the mass percent of the fusion cake powder is as follows: 50-60% of antibacterial agent and 40-50% of antibacterial agent; preferably, the frit has a chemical composition comprising: by mass percent, siO 2 ：38～42％、Al 2 O 3 ：1～3％、CaO：11～14％、MgO：0.2～0.4％、K 2 O：0.1～0.3％、Na 2 O：10～13％、B 2 O 3 :28 to 32 percent; the chemical composition of the antibacterial agent comprises: in percentage by mass, na 2 O：1～2％、P 2 O 5 ：11～13％、Ag：0.5～0.7％、SiO 2 ：1～3％、CaO：28～30％、MgO：0.1～0.3％、ZnO：17～18％、ZrO 2 : 14-15%, loss on ignition: 21 to 24 percent.
Preferably, the corundum has a mesh number of 325-400 meshes.
Preferably, before the anti-slip glaze is applied to the surface of the green brick, a surface glaze is applied to the surface of the green brick, and the pattern is printed by ink jet and a protective glaze is applied.
In a second aspect, the invention also provides an antibacterial and antiskid ceramic tile obtained by the preparation method. The antibacterial rate of escherichia coli and the antibacterial rate of staphylococcus aureus of the antibacterial and anti-skid ceramic tile are both more than 95%, and the dry friction coefficient and the wet friction coefficient are both more than 0.9.
Drawings
FIG. 1 is a diagram of the effect of the antibacterial and anti-slip ceramic tile of embodiment 1 on the surface of the tile with a magnification of 100 times under a light mirror.
FIG. 2 is a diagram showing the effect of the antibacterial and anti-slip ceramic tile of comparative example 1 on the surface of the tile with a magnification of 100 times under a light mirror.
FIG. 3 is a diagram showing the effect of the antibacterial and anti-slip ceramic tile of comparative example 2 on the surface of the tile with a magnification of 100 times under a light mirror.
FIG. 4 is a diagram showing the effect of the antibacterial and anti-slip ceramic tile of comparative example 3 on the surface of the tile with a magnification of 100 times under a light mirror.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage refers to a mass percentage.
The following illustrates the preparation method of the antibacterial and anti-slip ceramic tile.
And forming the green body powder to obtain a green brick. Can be formed by dry pressing by a press. The composition of the green body powder is not limited, and the conventional ceramic tile green body powder in the field can be adopted. For example, the chemical composition of the green body powder comprises, in mass percent, siO 2 ：63.2～65.1％、Al 2 O 3 ：20～23％、Fe 2 O 3 ：0.4～0.8％、TiO 2 ：0.2～0.3％、CaO：0.2～0.3％、MgO：0.4～0.60％、K 2 O：2.2～2.6％、Na 2 O: 2.1-2.6%, loss on ignition: 4.4 to 5.4 percent.
And drying the green brick. The water content of the dried green brick is controlled to be 0.3-0.4 wt%. The drying time may be 70 to 80 minutes.
And (4) preparing the overglaze. The chemical composition of the overglaze can comprise: by mass percent, siO 2 ：61.90～64.15％、Al 2 O 3 ：19.78～22.08％、Fe 2 O 3 ：0.22～0.4％、TiO 2 ：0.15～0.25％、CaO：0.20～0.4％、MgO：0.1～0.2％、K 2 O：3～4％、Na 2 O：3.15～3.77％、ZrO 2 : 3.2-9.6%, loss on ignition: 1.50 to 2.0 percent.
The raw material composition of the overglaze can comprise; potassium feldspar powder: 28-35%, albite: 15 to 21 percent of kaolin 12 to 18 percent, 12 to 18 percent of quartz sand, 8 to 12 percent of zirconium silicate, 5 to 9 percent of alumina and 3 to 8 percent of calcined kaolin.
By way of example, the overglaze comprises the following raw materials: potassium feldspar powder: 30%, albite: 18 percent of kaolin, 15 percent of quartz sand, 10 percent of zirconium silicate, 7 percent of alumina and 5 percent of calcined kaolin.
And mixing the overglaze according to the mixture ratio of the raw materials, ball-milling and sieving to obtain overglaze slip. In the process of ball milling, auxiliary materials and water are added into the mixed raw materials. In some embodiments, the formulation of the overglaze slip is: by mass percentage, the dry overglaze material (namely all overglaze raw materials) is 70 percent, the sodium tripolyphosphate is 0.25 percent, the sodium carboxymethyl cellulose is 0.15 percent, and the water is 29.75 percent. The 325-mesh screen residue of the overglaze is less than or equal to 0.6wt%.
The overglaze can be applied by adopting a glaze spraying or glaze pouring mode. The specific gravity of the overglaze can be 1.40-1.50 g/cm 3 The glazing amount can be 450-650 g/m 2 。
And printing a pattern on the surface of the green brick after the overglaze is applied by ink jet. The color and pattern of the inkjet printed pattern vary according to the layout effect.
And preparing the protective glaze.
The chemical composition of the protective glaze may include: by mass percent, siO 2 ：45～50％、Al 2 O 3 ：18～22％、Fe 2 O 3 ：0.08～0.15％、TiO 2 ：0.1～0.2％、CaO：0.1～0.3％、MgO：4～6％、BaO：10～13％、ZnO：2～4％、K 2 O：4～5％、Na 2 O: 1-2%, loss on ignition: 4 to 6 percent.
As an example, the chemical composition of the protective glaze includes: by mass percent, siO 2 ：48.47％、Al 2 O 3 ：20.59％、Fe 2 O 3 ：0.11％、TiO 2 ：0.15％、CaO：0.2％、MgO：4.93％、BaO：11.69％、ZnO：2.98％、K 2 O：4.38％、Na 2 O:1.48%, loss on ignition: 4.97 percent.
The raw material composition of the protective glaze can comprise: by mass percentage, 37-43% of potassium feldspar powder, 2-4% of zinc oxide, 13-17% of barium carbonate, 13-18% of calcined talc, 13-18% of kaolin, 2-4% of calcined kaolin, and alumina: 3 to 5 percent.
By way of example, the raw material composition of the protective glaze comprises: by mass percentage, potassium feldspar powder 40%, zinc oxide 3%, barium carbonate 15%, calcined talc 15%, kaolin 15%, calcined kaolin 3%, alumina: 4 percent.
And mixing the protective glaze according to the proportion of the raw materials, ball-milling and sieving to obtain the protective glaze slip. In the ball milling process, auxiliary materials and water are added into the mixed raw materials. In some embodiments, the ratio of the protective glaze slip is: by mass percentage, 70% of dry protective glaze (namely all protective glaze), 0.25% of sodium tripolyphosphate, 0.15% of sodium carboxymethylcellulose and 29.75% of water. The 325-mesh sieve residue of the protective glaze is less than or equal to 0.6wt%.
The protective glaze can be glazed by adopting a glaze spraying mode. The specific gravity of the protective glaze can be 1.30-1.35 g/cm 3 The glazing amount can be 240-270 g/m 2 。
And preparing the anti-slip glaze. The raw material composition of the antiskid glaze is corundum. The corundum has 325-400 meshes. Preferably 325 mesh. The use of 325-400 mesh corundum in the anti-skid glaze can obtain higher anti-skid performance, and the corundum is thinner, so that the hand feeling is not too rough. It is to be noted that corundum cannot be directly added to the protective glaze or the below-described antibacterial glaze in the present invention. If the corundum with the mesh number is directly added into the protective glaze, the antiskid effect is obviously reduced because: firstly, the corundum with smaller mesh number can lose the anti-skid effect by the reaction of partial corundum and protective glaze; secondly, corundum must be exposed on the surface of the protective glaze to have the anti-skid effect. If the corundum is directly added into the protective glaze, a large amount of corundum is positioned in the middle and lower layers of the protective glaze due to the large application amount of the protective glaze, so that the amount of corundum exposed on the protective glaze is small, and the antiskid effect is reduced. If the corundum is added into the antibacterial glaze for use, the firing temperature of the corundum is up to above 1300 ℃, and the eutectic temperature of the corundum and the antibacterial glaze is far higher than the firing temperature (650-750 ℃) of the antibacterial glaze, so that the corundum and the antibacterial glaze cannot be fused together basically under the firing condition of the antibacterial glaze (i.e. firing at the second stage), and the corundum and the antibacterial glaze cannot be integrated, so that the adhesion of the corundum in the antibacterial glaze is poor, and the anti-skid and wear-resistant properties of the brick surface are obviously reduced.
The chemical composition of the anti-slip glaze can comprise: by mass percent, siO 2 ：0.35～0.58％、Al 2 O 3 ：98.92～99.52％，Na 2 O: 0.20-0.38%, loss on ignition: 0.1 to 0.2 percent.
The preparation process of the anti-slip glaze does not need ball milling. During preparation, the raw materials can be prepared according to the following mixture ratio: 325 mesh corundum: 7-15%, dry glue: 85 to 93 percent.
And applying anti-slip glaze on the surface of the green brick after spraying the protective glaze. The anti-slip glaze can be glazed by adopting a glaze spraying mode. The specific gravity of the anti-slip glaze can be 1.10-1.15 g/cm 3 The glazing amount can be 60-80 g/m 2 . The application amount of the anti-slip glaze can ensure excellent anti-slip effect.
And sintering the green bricks after the anti-slip glaze is applied in the first stage. The highest temperature of the first stage sintering is 1200-1220 ℃, and the sintering period is 50-60 min.
And (4) preparing the antibacterial glaze. The chemical composition of the antibacterial glaze can comprise: by mass percent, siO 2 ：21～26％、Al 2 O 3 ：1.0～1.5％、CaO：18～21％、MgO：0.2～0.3％、K 2 O：0.2～0.3％、Na 2 O：6～8％、B 2 O 3 ：15～19％、P 2 O 5 ：4～6％、Ag：0.20～0.30％、ZnO：6～8％、ZrO 2 : 5-7%, loss on ignition: 8.8 to 12 percent. The melting starting temperature of the antibacterial glaze is 500-550 ℃. In the preparation method of the present invention, the temperature at which the antibacterial glaze is applied needs to be higher than the melting temperature of the antibacterial glaze, which causes the antibacterial glaze to start melting to form a vitreous body. The glass body formed by the antibacterial glaze bonds the protective glaze, the corundum and the antibacterial glaze together, so that the antibacterial glaze is firmly fixed on the ceramic tile. In addition, the application amount of the antibacterial glaze is small, so that the thickness of the antibacterial glaze layer can be ignored, and corundum cannot be covered, so that the influence on the anti-skid performance is avoided.
In some embodiments, the raw material composition of the antibacterial glaze comprises: the fusion cake comprises the following components in percentage by mass: 50-60% of antibacterial agent and 40-50% of antibacterial agent. The frit content is too low to be beneficial to the fusion and fixation of the antibacterial glaze. The frit content is too high, and the antibacterial effect of the antibacterial glaze is low. The clinker powder and the antibacterial agent are each independently selected to be 325 mesh or larger.
The formation of the antibacterial in-glaze glass body is mainly controlled by the antibacterial in-glaze frit. Because the frit is subjected to high-temperature smelting in the process of preparing the frit, and the melting point of the frit is 500-550 ℃, the frit starts to form a glass body when the temperature reaches above 500 ℃ in the process of preparing the ceramic tile, and the frit is basically in a molten state along with the increase of the temperature, and the unmelted antibacterial agent can be bonded with the ceramic tile by the molten glass body. In tests, the frit content of more than 50% can realize the firm combination of the antibacterial glaze and the corundum. In some embodiments, the frit has a chemical composition comprising: in terms of mass percent, siO 2 ：38～42％、Al 2 O 3 ：1～3％、CaO：11～14％、MgO：0.2～0.4％、K 2 O：0.1～0.3％、Na 2 O：10～13％、B 2 O 3 :28 to 32 percent. As an example, the chemical composition of the frit includes: by mass percent, siO 2 ：40.75％、Al 2 O 3 ：2.49％、CaO：12.77％、MgO：0.32％、K 2 O：0.26％、Na 2 O：11.84％、B 2 O 3 ：30.71％。
The chemical composition of the antibacterial agent comprises: in percentage by mass, na 2 O：1～2％、P 2 O 5 ：11～13％、Ag：0.5～0.7％、SiO 2 ：1～3％、CaO：28～30％、MgO：0.1～0.3％、ZnO：17～18％、ZrO 2 : 14-15%, loss on ignition: 21 to 24 percent. As an example, the chemical composition of the above antibacterial agent includes: in percentage by mass, na 2 O：1.33％、P 2 O 5 ：12.2％、Ag：0.56％、SiO 2 ：1.9％、CaO：29.10％、MgO：0.19％、ZnO：17.40％、ZrO 2 :14.60%, loss on ignition: 22.50 percent.
The antibacterial agent comprises the following raw materials: the silver-carrying zirconium sodium phosphate antibacterial agent comprises the following components in percentage by mass: 30-40%, nano zinc oxide: 15-20%, calcium carbonate: 30-40%, albite powder: 15 to 25 percent. Because the sintering temperature of the sodium zirconium phosphate silver-loaded antibacterial agent and the nano zinc oxide is higher, the sintering temperature of the antibacterial agent can be reduced by adding the calcium carbonate and the albite powder.
Mixing the zirconium sodium phosphate silver-loaded antibacterial agent with nano zinc oxide, calcium carbonate and albite powder, ball-milling, and sieving with a 325-mesh sieve to obtain the antibacterial agent. The sodium zirconium phosphate silver-carrying antibacterial agent can be obtained from the market or the self-made. For example, the sodium zirconium phosphate silver-loaded antimicrobial agent is prepared by the following steps: and (1) mixing the raw materials. Weighing a certain amount of NaZr 2 (PO 4 ) 3 And AgNO 3 Mix and place in a three-neck flask and add deionized water. And (2) carrying out ion exchange reaction. And (3) placing the three-neck flask in an oil bath, heating to about 80 ℃, stirring reactants in the three-neck flask to fully react, controlling the pH value and ensuring the pH value to be about 6, wherein the reaction time is 6 hours. And (3) washing to remove impurities. Taking out the resultant (suspension), vacuum filtering with a filter funnel, and adding hydrochloric acid to the filtrate to test whether there is impurity Ag + If white precipitate is generated, it indicates that impurity Ag exists + Otherwise, there is no impurity Ag + (ii) a Taking out the residual solid, adding deionized water again, stirring with a glass rod, filtering, repeating the steps for several times until no Ag exists in the filtrate + . And (4) drying. The silver-carrying antibacterial agent is put into an oven to be dried, the drying temperature is 105 ℃, and the drying time is 20 hours. And (5) grinding. And (3) putting the dried silver antibacterial agent solid into a mortar, grinding for about 20 minutes, then putting into a ball mill, and ball-milling for 10 hours to finally obtain silver-containing antibacterial agent powder. And (6) calcining. And (3) placing the ground silver antibacterial agent into a muffle furnace for calcination at 800 ℃ for 12h to obtain zirconium sodium phosphate silver-loaded antibacterial agent powder.
Silver simple substance or silver ion in the silver antibacterial agent is easy to dissolve out and oxidize, so that the antibacterial effect is lost, and the surface of the zirconium sodium phosphate is in a porous structure, so that the zirconium sodium phosphate has the advantages of large specific surface area, strong adsorption capacity, good chemical stability and high temperature resistance, and can enable the loaded silver ion to generate good slow release effect. Therefore, the antibacterial agent is chemically treated so that silver ions are wrapped by sodium zirconium phosphate, and the antibacterial effect is better and more durable than that of the antibacterial agent directly using a mixture of silver powder and zinc oxide.
In some embodiments, the phase composition of the antimicrobial agent is zincite (ZnO): 15 to 20 percent of calcite (CaCO) 3 )：30～40％，NaZr 2 (PO 4 ) 3 ：30～40％，Na 2 (Hf(OH) 6 )：5～10％，Na 3.59 Mg 2.71 (PO 4 ) 3 : 2-5%, amorphous phase: 0 to 0.1 percent. For example, the phase composition of the antibacterial agent is a zincite (ZnO): 16.81% of calcite (CaCO) 3 )：36.58％，NaZr 2 (PO 4 ) 3 ：35.49％，Na 2 (Hf(OH) 6 )：7.31％，Na 3.59 Mg 2.71 (PO 4 ) 3 :3.81%, amorphous phase: 0.04 percent. Since silver ions are encapsulated in the crystals of sodium zirconium phosphate, no silver crystals are present in XRD.
The preparation process of the antibacterial glaze does not need ball milling. During preparation, the raw materials are prepared according to the following mixture ratio: 325 mesh clinker powder: 3-5%, 325 mesh antibacterial glaze powder: 3-5% of dry particle glue: 90 to 94 percent. The dry particle glue can provide enough suspensibility, so that the fusion cake powder and the antibacterial glaze powder do not precipitate, and provide enough moisture retention.
The top of the kiln is disassembled in a cooling zone with the temperature of the kiln of 650-750 ℃ and is used for spraying the antibacterial glaze. Namely, the temperature of the kiln is 650-750 ℃ when the antibacterial glaze is applied. The process can solve the problem that the antibacterial glaze powder cannot resist high temperature, the antibacterial glaze contains silver ions and nano zinc oxide, has double sterilization effects, is low in melting temperature, can firmly fix the antibacterial agent on the ceramic tile and well cover the anti-slip glaze, and further improves the hand feeling of the anti-slip glaze.
The requirement of glaze spraying at 650-750 ℃ on the glaze application environment is high, the defects of dirt falling and the like need to be noticed, and the glaze slip is ensured to be dried after being sprayed on the surface of the brick. The glaze spraying temperature is selected according to the principle that silver ions can be oxidized into silver oxide after the temperature of the silver glaze antibacterial glaze is higher than 800 ℃, zinc oxide can also react to lose the antibacterial effect, and the glaze material with too low temperature can not be melted to cause the antibacterial glaze to be attached insecurely and be easily cleaned.
The specific gravity of the antibacterial glaze can be 1.05-1.10 g/cm 3 The glazing amount can be 70-90 g/m 2 . The antibacterial glaze with the application amount has good antibacterial effect while the anti-skid effect is not obviously reduced.
It is worth mentioning that in the preparation method of the invention, the application positions of the antibacterial glaze and the anti-slip glaze can not be interchanged, because the antibacterial agent needs to be in contact with bacteria to play a role in sterilization, and if the antibacterial glaze is directly applied after the protective glaze is applied, the antibacterial agent is covered by the protective glaze so as to lose the sterilization function.
And finally, sintering the green brick after the antibacterial glaze is applied in the second stage. The highest temperature of the second stage sintering is 650-750 ℃, and the sintering period is 5-10 min. The purpose of the firing in the step is to uniformly and firmly fix the antibacterial glaze on the surface of the ceramic tile, and meanwhile, the firing temperature is low, so that the antibacterial glaze cannot lose the antibacterial effect.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The antibacterial property of the ceramic tile is detected according to JC/T897-2014-standard, the dry friction coefficient and the wet friction coefficient are detected according to GB/T4100-2015, and the pollution resistance is detected according to GB/T3810.13-2017.
EXAMPLE 1
Step 1, forming the green body powder by using a press to obtain a green brick.
And 2, drying the green bricks.
And 3, spraying surface glaze on the surface of the dried green brick. The overglaze comprises the following chemical components: siO 2 2 ：62.90％、Al 2 O 3 ：21.08％、Fe 2 O 3 ：0.26％、TiO 2 ：0.19％、CaO：0.28％、MgO：0.13％、K 2 O：3.88％、Na 2 O：3.35％、ZrO 2 :7.2%, loss on ignition: 1.80 percent. The specific gravity of the overglaze is 1.45g/cm 3 The glazing amount is 500g/m 2 。
And 4, ink-jetting and printing patterns on the surface of the green brick sprayed with the cover glaze.
And 5, spraying protective glaze on the surface of the green brick after the pattern is printed by ink jet. The chemical composition of the protective glaze comprises: by mass percent, siO 2 ：48.47％、Al 2 O 3 ：20.59％、Fe 2 O 3 ：0.11％、TiO 2 ：0.15％、CaO：0.2％、MgO：4.93％、BaO：11.69％、ZnO：2.98％、K 2 O：4.38％、Na 2 O:1.48%, loss on ignition: 4.97 percent. The specific gravity of the protective glaze is 1.30g/cm 3 The glazing amount is 260g/m 2 。
And 6, spraying anti-slip glaze on the surface of the green brick sprayed with the protective glaze. The raw material composition of the antiskid glaze is 325 meshes of corundum. The specific gravity of the anti-slip glaze is 1.12g/cm 3 The glazing amount is 70g/m 2 。
And 7, sintering the brick blank sprayed with the anti-slip glaze in the first stage. The highest temperature of the first stage sintering is 1200-1220 ℃, and the sintering period is 50-60 min. After the first stage of sintering, the top of the kiln is disassembled (at the moment, the temperature of the kiln is 650-750 ℃) and is used for spraying the antibacterial glaze.
And 8, spraying the antibacterial glaze. The antibacterial glaze comprises the following raw materials: the mass percent of the fusion cake powder is as follows: 60 percent and 40 percent of antibacterial agent. The chemical composition of the antibacterial glaze comprises: by mass percent, siO 2 ：25.21％、Al 2 O 3 ：1.49％、CaO：19.30％、MgO：0.27％、K 2 O：0.22％、Na 2 O：7.64％、B 2 O 3 ：18.43％。P 2 O 5 ：4.88％、Ag：0.22％、ZnO：6.96％、ZrO 2 :5.84%, loss on ignition: 9.0 percent. The specific gravity of the antibacterial glaze is 1.08g/cm 3 The glazing amount is 80g/m 2 。
And 9, sintering the green brick sprayed with the antibacterial glaze in a second stage to obtain the antibacterial and antiskid ceramic brick. Wherein the highest temperature of the second stage sintering is 650-750 ℃, and the sintering period is 5-10 min.
The glazed ceramic tile has weak granular feeling, small particle size, uniform distribution (as shown in figure 1) and rough hand feeling. The antibacterial rate of escherichia coli of the ceramic tile is 99.2%, the antibacterial rate of staphylococcus aureus is 99.5%, the dry static friction coefficient is 0.95, the wet static friction coefficient is 0.93, and the ceramic tile is antifouling class A.
Comparative example 1
Essentially the same as example 1, except that:
and step 1, molding the green body powder by using a press to obtain a green brick.
And 2, drying the green bricks.
And 3, spraying surface glaze on the surface of the dried green brick. The overglaze comprises the following chemical components: siO 2 2 ：62.90％、Al 2 O 3 ：21.08％、Fe 2 O 3 ：0.26％、TiO 2 ：0.19％、CaO：0.28％、MgO：0.13％、K 2 O：3.88％、Na 2 O：3.35％、ZrO 2 :7.2%, loss on ignition: 1.80 percent. The specific gravity of the overglaze is 1.45g/cm 3 The glazing amount is 500g/m 2 。
And 4, ink-jet printing patterns on the surface of the green brick sprayed with the overglaze.
And 5, spraying protective glaze on the surface of the green brick after the pattern is printed by ink jet. The chemical composition of the protective glaze comprises: by mass percent, siO 2 ：48.47％、Al 2 O 3 ：20.59％、Fe 2 O 3 ：0.11％、TiO 2 ：0.15％、CaO：0.2％、MgO：4.93％、BaO：11.69％、ZnO：2.98％、K 2 O：4.38％、Na 2 O:1.48%, loss on ignition: 4.97 percent. The specific gravity of the protective glaze is 1.30g/cm 3 The glazing amount is 260g/m 2 。
And 6, spraying anti-slip glaze on the surface of the green brick sprayed with the protective glaze. The raw material composition of the antiskid glaze is 325 meshes of corundum. The specific gravity of the anti-slip glaze is 1.12g/cm 3 The glazing amount is 70g/m 2 。
And 7: spraying the anti-slip glaze, drying, directly spraying the antibacterial glaze, and then sintering. The antibacterial glaze comprises the following raw materials: the mass percent of the fusion cake powder is as follows: 60 percent and 40 percent of antibacterial agent. The chemical composition of the antibacterial glaze comprises: by mass percent, siO 2 ：25.21％、Al 2 O 3 ：1.49％、CaO：19.30％、MgO：0.27％、K 2 O：0.22％、Na 2 O：7.64％、B 2 O 3 ：18.43％。P 2 O 5 ：4.88％、Ag：0.22％、ZnO：6.96％、ZrO 2 :5.84%, loss on ignition: 9.0 percent. The specific gravity of the antibacterial glaze is 1.08g/cm 3 The glazing amount is 80g/m 2 . The highest temperature of the sintering is 1200-1220 ℃, and the sintering period is 60-70 min.
The glazed surface of the ceramic tile has weak granular feeling, small particle size, uniform distribution (as shown in figure 2) and rough hand feeling. The antibacterial rate of Escherichia coli of the ceramic tile is 22.1%, the antibacterial rate of Staphylococcus aureus is 25.2%, the dry static friction coefficient is 0.92, the wet static friction coefficient is 0.90, and the ceramic tile is antifouling class A. It can be seen that the antibacterial effect of the ceramic tile is remarkably reduced due to the over-high firing temperature.
Comparative example 2
Essentially the same as example 1, except that:
step 1, forming the green body powder by using a press to obtain a green brick.
And 2, drying the green bricks.
And 3, spraying surface glaze on the surface of the dried green brick. The overglaze comprises the following chemical components: siO 2 2 ：62.90％、Al 2 O 3 ：21.08％、Fe 2 O 3 ：0.26％、TiO 2 ：0.19％、CaO：0.28％、MgO：0.13％、K 2 O：3.88％、Na 2 O：3.35％、ZrO 2 :7.2%, loss on ignition: 1.80 percent. The specific gravity of the overglaze is 1.45g/cm 3 The glazing amount is 500g/m 2 。
And 4, ink-jetting and printing patterns on the surface of the green brick sprayed with the cover glaze.
And 5, spraying protective glaze on the surface of the green brick after the pattern is printed by ink jet. The chemical composition of the protective glaze comprises: in terms of mass percent, siO 2 ：46.27％、Al 2 O 3 ：22.79％、Fe 2 O 3 ：0.09％、TiO 2 ：0.15％、CaO：0.2％、MgO：4.93％、BaO：11.69％、ZnO：2.98％、K 2 O：4.38％、Na 2 O:1.48%, loss on ignition: 4.95 percent. The specific gravity of the protective glaze is 1.30g/cm 3 The glazing amount is 260g/m 2 。
And 6, sintering the green bricks sprayed with the protective glaze in the first stage. The highest temperature of the first stage sintering is 1200-1220 ℃, and the sintering period is 60-70 min. After the first stage of sintering is finished, the top of the kiln is disassembled (at the moment, the temperature of the kiln is 650-750 ℃) and is used for spraying the antibacterial glaze.
And 7, spraying the antibacterial glaze. The antibacterial glaze comprises the following raw materials: the method comprises the following steps of (1) melting block powder: 60 percent and 40 percent of antibacterial agent. The chemical composition of the antibacterial glaze comprises: in terms of mass percent, siO 2 ：25.21％、Al 2 O 3 ：1.49％、CaO：19.30％、MgO：0.27％、K 2 O：0.22％、Na 2 O：7.64％、B 2 O 3 ：18.43％。P 2 O 5 ：4.88％、Ag：0.22％、ZnO：6.96％、ZrO 2 :5.84%, loss on ignition: 9.0 percent. The specific gravity of the antibacterial glaze is 1.08g/cm 3 The glazing amount is 80g/m 2 。
And 8, sintering the green brick sprayed with the antibacterial glaze in a second stage to obtain the antibacterial and antiskid ceramic tile. Wherein the highest temperature of the second stage sintering is 650-750 ℃, and the sintering period is 5-10 min.
The glazed surface of the ceramic tile is granular and feeble, and has smooth hand feeling (as shown in figure 3). The antibacterial rate of escherichia coli of the ceramic tile is 99.2%, the antibacterial rate of staphylococcus aureus is 99.5%, the dry static friction coefficient is 0.61, the wet static friction coefficient is 0.55, and the ceramic tile is antifouling grade A.
Comparative example 3
Essentially the same as example 1, except that: the glaze applying amount of the antibacterial glaze is different and is 120g/m 2 。
The glazed grain feel of the ceramic tile is weak (as shown in fig. 4). The antibacterial rate of escherichia coli of the ceramic tile is greater than 99.9%, the antibacterial rate of staphylococcus aureus is greater than 99.9%, the dry static friction coefficient is 0.77, the wet static friction coefficient is 0.65, and the ceramic tile is antifouling class A. The reason for the reduced anti-slip performance of the ceramic tile is that the antibacterial glaze is applied with too much glaze, and the corundum is covered by the antibacterial glaze, so that the exposed corundum is reduced.
Claims (6)
1. The preparation method of the antibacterial and antiskid ceramic tile is characterized by comprising the following steps:
applying surface glaze, ink-jet printing pattern and protective glaze on the surface of the green brick;
then, applying anti-slip glaze on the surface of the green brick, wherein the mineral composition of the anti-slip glaze is corundum, and the mesh number of the corundum is 325-400 meshes;
sintering the green brick after the anti-slip glaze is applied in the first stage; the highest temperature of the first stage sintering is 1200 to 1220 ℃, and the sintering period is 50 to 60min;
after the first stage of firing is finished, the top of the kiln is disassembled in a cooling area with the temperature of the kiln ranging from 650 to 750 ℃ and is used for spraying antibacterial glaze; the antibacterial glaze comprises the following raw materials: the fusion cake comprises the following components in percentage by mass: 50 to 60 percent of antibacterial agent and 40 to 50 percent of antibacterial agent; the frit comprises the following chemical compositions: in terms of mass percent, siO 2 ：38～42%、Al 2 O 3 ：1～3%、CaO：11～14%、MgO：0.2～0.4%、K 2 O：0.1～0.3%、Na 2 O：10～13%、B 2 O 3 :28 to 32 percent; the antibacterial agent comprises the following raw materials: the silver-carrying zirconium sodium phosphate antibacterial agent comprises the following components in percentage by mass: 30 to 40 percent, nano zinc oxide: 15 to 20%, calcium carbonate: 30 to 40% and albite powder: 15 to 25 percent; the application mode of the antibacterial glaze is glaze spraying, and the specific gravity of the antibacterial glaze is 1.05 to 1.10g/cm 3 The glazing amount is 70 to 90g/m 2 ；
Sintering the green brick applied with the antibacterial glaze in the second stage to enable the antibacterial glaze to be molten, and firmly combining the antibacterial glaze and the anti-slip glaze and fixing the antibacterial glaze and the anti-slip glaze on the surface of the green brick to obtain the antibacterial anti-slip ceramic brick; the maximum temperature of the second stage sintering is 650 to 750 ℃, and the sintering period is 5 to 10min.
2. The preparation method according to claim 1, wherein the anti-slip glaze is applied in a glaze spraying manner, and the specific gravity of the anti-slip glaze is 1.10 to 1.15g/cm 3 The glazing amount is 60 to 80g/m 2 。
3. The preparation method according to claim 1, wherein the chemical composition of the antibacterial glaze comprises: in terms of mass percent, siO 2 ：21~26%、Al 2 O 3 ：1.0~1.5%、CaO：18~21%、MgO：0.2~0.3%、K 2 O：0.2~0.3%、Na 2 O：6~8%、B 2 O 3 ：15~19%、P 2 O 5 ：4~6%、Ag：0.20~0.30%、ZnO：6~8%、ZrO 2 :5 to 7 percent, loss on ignition: 8.8 to 12 percent.
4. The preparation method according to claim 1, wherein the melting temperature of the antibacterial glaze is 500 to 550 ℃.
5. The method of claim 1, wherein the chemical composition of the antimicrobial agent comprises: in percentage by mass, na 2 O：1～2%、P 2 O 5 ： 11～13%、Ag：0.5～0.7%、SiO 2 ：1～3%、CaO：28～30%、MgO：0.1～0.3%、ZnO：17～18%、ZrO 2 : 14-15%, loss on ignition: 21 to 24 percent.
6. The antibacterial and anti-slip ceramic tile obtained by the preparation method according to any one of claims 1 to 5, wherein the antibacterial rate of Escherichia coli and the antibacterial rate of Staphylococcus aureus of the antibacterial and anti-slip ceramic tile are both above 95%, and the dry friction coefficient and the wet friction coefficient are both above 0.9.
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