阅读说明：本技术 一种防污抗菌陶瓷釉料 (Antifouling antibacterial ceramic glaze ) 是由 韩彦 于 2019-12-06 设计创作，主要内容包括：本发明提供了一种防污抗菌陶瓷釉料,涉及特种功能陶瓷釉料技术领域。本发明的防污抗菌陶瓷釉料防污抗菌材料、陶瓷釉料基料、减水剂按照重量比8:3:2混合制备而成,为了解决现有的载银抗菌陶瓷制品,成本高、仅具有抗菌作用而不具有防污作用的技术问题,因此本发明提供了一种防污抗菌陶瓷釉料,该防污抗菌陶瓷釉料具有光泽度好、色泽鲜艳,用本发明制备的防污抗菌陶瓷釉料生产的陶瓷,具有显著的多孔性能以及良好的抗张强度和硬度,抗菌效果和防污效果显著,而且本发明制备的防污陶瓷釉料,不含铅,更加绿色环保,尤其适用于碗、碟等厨具陶瓷釉料配方,由于不含银离子,长时间使用不易变黑变黄。(The invention provides an antifouling and antibacterial ceramic glaze, and relates to the technical field of special functional ceramic glazes. The antifouling antibacterial ceramic glaze material, the ceramic glaze base material and the water reducing agent are prepared by mixing according to the weight ratio of 8:3:2, and in order to solve the technical problems that the existing silver-loaded antibacterial ceramic product is high in cost and only has an antibacterial effect but not an antifouling effect, the antifouling antibacterial ceramic glaze material is provided.)

1. An antifouling antibacterial ceramic glaze is prepared by mixing an antifouling antibacterial material, a ceramic glaze base material and a water reducing agent according to a weight ratio of 8:3: 2; the method is characterized in that:

the ceramic glaze base material consists of the following raw materials in parts by weight: 3-11 parts of pyrophyllite, 1-5 parts of spodumene, 3-20 parts of cordierite, 12-18 parts of andalusite, 5-9 parts of medical stone, 4-10 parts of nano zinc oxide, 3-8 parts of nano aluminum oxide, 3-7 parts of nano zirconium oxide and 5-7 parts of nano boron oxide;

the weight ratio of spodumene to cordierite is 3: 4;

the water reducing agent is prepared from the following raw materials in parts by weight: 1-3 parts of sodium dodecyl benzene sulfonate, 1-2 parts of sodium alginate and 1-4 parts of sodium citrate;

the antifouling antibacterial material is prepared from the following raw materials in parts by weight: 10-15 parts of ginger powder, 1.8-3.6 parts of dodecyl betaine, 3-6 parts of capsaicin, 1-4 parts of graphene oxide, 8-10 parts of polyurethane and a proper amount of 80% ethanol by mass concentration.

2. The anti-fouling antibacterial ceramic glaze according to claim 1, wherein: the preparation method comprises the following steps:

① mixing pyrophyllite, spodumene, cordierite, andalusite and medical stone in parts by weight, crushing, sieving with a 120-mesh sieve to obtain a mixture A, adding nano zinc oxide, nano alumina, nano zirconia and nano boron oxide into the mixture A, uniformly mixing to obtain a mixture B, adding water into the mixture B, ball-milling until the mixture B is sieved with a 200-mesh sieve, drying, and carrying out jet milling to obtain a ceramic glaze base material;

② mixing ginger powder, dodecyl betaine, capsaicin and graphene oxide in parts by weight, crushing, sieving with a 300-mesh sieve, mixing with polyurethane, performing ultrasonic oscillation for 10-15min to obtain an ultrasonic mixture D, uniformly mixing the ultrasonic mixture D with 80% ethanol in a weight ratio of 2: 5, heating to 60-65 ℃, stirring for 40-50min, and then performing reduced pressure distillation to remove an ethanol solvent to obtain the antifouling and antibacterial material;

③ mixing the sodium dodecyl benzene sulfonate, the sodium alginate and the sodium citrate uniformly, calcining at the temperature of 500-1000 ℃ for 20-30min, taking out, cooling to room temperature, crushing and sieving with a 200-mesh sieve to obtain the water reducer;

④ mixing the prepared ceramic glaze base material, the antifouling and antibacterial material and the water reducing agent, putting the mixture into a muffle furnace to be fully melted at the temperature of 1000-1300 ℃, drying after water quenching to obtain ceramic frit, and then mixing the ceramic frit, the ball stone and water according to the weight ratio of 3:7:1 into a ball mill to be ball-milled until the fineness of the slurry is 400 meshes, thus obtaining the antifouling and antibacterial ceramic glaze.

3. The anti-fouling antibacterial ceramic glaze according to claim 1, wherein: the weight ratio of sodium dodecyl benzene sulfonate, sodium alginate and sodium citrate in the water reducing agent is 2:1.5: 2.5.

4. The anti-fouling antibacterial ceramic glaze according to claim 1, wherein: the weight ratio of graphene oxide to dodecyl betaine in the antifouling and antibacterial material is 2.5: 2.4.

Technical Field

The invention relates to the technical field of special functional ceramic glaze, in particular to an antifouling antibacterial ceramic glaze.

Background

The ceramic is made up by using natural clay and various natural minerals as main raw materials and making them pass through such processes of pulverizing, mixing, forming and calcining. In recent years, the daily ceramic industry in China has been developed greatly, and the yield of daily ceramic is at the forefront of the world at present. Because the microstructure of the ceramic material consists of a crystal phase, a glass phase and air holes, the porosity of a final product exists between 5 percent and 10 percent (volume), meanwhile, the surface of the ceramic material has certain lipophilicity, when pollutants contact the surface of the product, a part of the pollutants are deeply inserted into the open air holes due to the surface capillary action; in addition, microscopic irregularities in the ceramic surface also lead to adhesion to contaminants. The pollutants are basically composed of soluble colored inorganic matters or organic matters in water, are usually acidic or alkaline, such as sewage, tea water, dust, ink, organic oil stains and the like in daily life, so that the surface of the ceramic is polluted and difficult to clean, and the cleanness and the attractiveness are influenced. The accumulated oil stain can become a hotbed for breeding bacteria, and if the hotbed is not cleaned, the ceramic in a room becomes a virus and bacteria infection source.

The antibacterial ceramic is prepared by adding an inorganic antibacterial agent into ceramic glaze, and the inorganic antibacterial agents which are most widely researched and applied at present are of two types: the method is mainly characterized by high safety, difficult volatilization and decomposition, good heat resistance, belongs to a broad-spectrum antibacterial agent, long service life, no toxicity and convenient use, is most researched and applied at home and abroad at present, but generally has large silver addition amount and high product cost, and is difficult to be accepted by wide consumers. Meanwhile, with the wide use of ceramics in modern daily life of people, the requirements of people on daily ceramics are higher and higher, people pay more attention to environmental sanitation and body health, and therefore, the antifouling functional ceramics are more and more concerned.

The invention aims to provide an antifouling antibacterial ceramic glaze, which aims to solve the technical problems that the existing silver-loaded antibacterial ceramic product is high in cost and only has an antibacterial effect but not an antifouling effect

In order to achieve the purpose, the invention provides an antifouling and antibacterial ceramic glaze.

The antifouling and antibacterial ceramic glaze is prepared by mixing an antifouling and antibacterial material, a ceramic glaze base material and a water reducing agent according to a weight ratio of 8:3: 2.

Further, the ceramic glaze base material consists of the following raw materials in parts by weight: 3-11 parts of pyrophyllite, 1-5 parts of spodumene, 3-20 parts of cordierite, 12-18 parts of andalusite, 5-9 parts of medical stone, 4-10 parts of nano zinc oxide, 3-8 parts of nano aluminum oxide, 3-7 parts of nano zirconium oxide and 5-7 parts of nano boron oxide.

Further, the water reducing agent is prepared from the following raw materials in parts by weight: 1-3 parts of sodium dodecyl benzene sulfonate, 1-2 parts of sodium alginate and 1-4 parts of sodium citrate.

Further, the antifouling and antibacterial material is prepared from the following raw materials in parts by weight: 10-15 parts of ginger powder, 1.8-3.6 parts of dodecyl betaine, 3-6 parts of capsaicin, 1-4 parts of graphene oxide, 8-10 parts of polyurethane and a proper amount of 80% ethanol by mass concentration.

Further, the weight ratio of spodumene to cordierite is 3: 4.

Furthermore, the weight ratio of sodium dodecyl benzene sulfonate, sodium alginate and sodium citrate in the water reducing agent is 2:1.5: 2.5.

Furthermore, the weight ratio of the graphene oxide to the dodecyl betaine in the antifouling and antibacterial material is 2.5: 2.4.

Further, the preparation method of the antifouling and antibacterial ceramic glaze comprises the following steps:

① mixing pyrophyllite, spodumene, cordierite, andalusite and medical stone in parts by weight, crushing, sieving with a 120-mesh sieve to obtain a mixture A, adding nano zinc oxide, nano alumina, nano zirconia and nano boron oxide into the mixture A, uniformly mixing to obtain a mixture B, adding water into the mixture B, ball-milling until the mixture B is sieved with a 200-mesh sieve, drying, and carrying out jet milling to obtain a ceramic glaze base material;

② mixing ginger powder, dodecyl betaine, capsaicin and graphene oxide in parts by weight, crushing, sieving with a 300-mesh sieve, mixing with polyurethane, performing ultrasonic oscillation for 10-15min to obtain an ultrasonic mixture D, uniformly mixing the ultrasonic mixture D with 80% ethanol in a weight ratio of 2: 5, heating to 60-65 ℃, stirring for 40-50min, and then performing reduced pressure distillation to remove an ethanol solvent to obtain the antifouling and antibacterial material;

③ mixing the sodium dodecyl benzene sulfonate, the sodium alginate and the sodium citrate uniformly, calcining at the temperature of 500-1000 ℃ for 20-30min, taking out, cooling to room temperature, crushing and sieving with a 200-mesh sieve to obtain the water reducer;

④ mixing the prepared ceramic glaze base material, the antifouling and antibacterial material and the water reducing agent, putting the mixture into a muffle furnace to be fully melted at the temperature of 1000-1300 ℃, drying after water quenching to obtain ceramic frit, and then mixing the ceramic frit, the ball stone and water according to the weight ratio of 3:7:1 into a ball mill to be ball-milled until the fineness of the slurry is 400 meshes, thus obtaining the antifouling and antibacterial ceramic glaze.

The invention has the following beneficial effects:

1. the antifouling antibacterial ceramic glaze prepared by the invention has good glossiness and bright color, the ceramic produced by the antifouling antibacterial ceramic glaze prepared by the invention has obvious porous performance, good tensile strength and hardness, and obvious antibacterial effect and antifouling effect, and the antifouling ceramic glaze prepared by the invention does not contain lead, is more environment-friendly, is especially suitable for the formula of the ceramic glaze for kitchenware such as bowls, dishes and the like, and is difficult to turn black and yellow after being used for a long time because of not containing silver ions. The preparation process is simple, the conditions are easy to control, the production cost is low, and the industrial production is easy to realize.

2. When the sodium dodecyl benzene sulfonate, the sodium alginate and the sodium citrate are compounded, the sodium dodecyl benzene sulfonate belongs to the excessive addition of the starch-based water reducing agent, and the addition amount of the sodium alginate and the sodium citrate is too small, because the relative mass of the sodium dodecyl benzene sulfonate is large and the quantity of sulfonic acid groups in each molecule is small, the composite water reducing agent cannot be well extended in water, and the steric hindrance effect is poor, the flowability, the suspensibility and the stability of the glaze are greatly reduced, when the addition amount of the sodium dodecyl benzene sulfonate is too small and the addition amounts of the sodium alginate and the sodium citrate are too large, the viscosity of the ceramic glaze is increased, the stability is poor, the delamination is easy, and the surface activity effect of the compound water reducing agent is weakened, so when the sodium dodecyl benzene sulfonate, the sodium alginate and the sodium citrate are compounded and added into the ceramic glaze according to the weight ratio of 2:1.5:2.5, the ceramic glaze has good flowability, is not easy to delaminate, and has good suspensibility and stability. According to verification, when the addition amount of the compound water reducing agent is consistent, the preferable sodium dodecyl benzene sulfonate, sodium alginate and sodium citrate are compounded and added into the ceramic glaze according to the weight ratio of 2:1.5:2.5, so that the outflow time of the ceramic glaze is 35s, the Zeta potential is-47.5 mV, and the water reducing effect is obvious.

3. Firstly, when the ceramic glaze base material is prepared, spodumene is used for replacing the traditional lead oxide, so that when the ceramic glaze is used for kitchen ware ceramics such as bowls, dishes and the like, the health of human bodies is ensured, the ceramic glaze is more green and environment-friendly, meanwhile, the thermal expansion coefficient of the ceramic glaze is reduced, and the blank glaze binding performance is improved. When the amount of spodumene added is too large and the amount of cordierite added is too small, the porosity of the fired ceramic is rapidly increased, the thermal expansion coefficient is increased, and the hardness and tensile strength of the ceramic are reduced, and when the amount of spodumene added is too small and the amount of cordierite added is too large, the porosity of the ceramic is rapidly reduced because the ceramic pores are completely filled with the excessive cordierite particles, and therefore, only when the weight ratio of spodumene to cordierite is 3:4, the tensile strength and hardness of the fired ceramic are significantly improved while the high porosity is maintained. The porosity reaches 49.21% when the weight ratio of spodumene to cordierite is 3: 4; the breaking strength is 23.17 MPa; the coefficient of thermal expansion is 1.66X 10-6/DEG C.

Secondly, pyrophyllite is added during preparation of the ceramic glaze base material, and a compact mineral matter protective layer is formed on the surface of the glaze by the pyrophyllite in the sintering process, so that on one hand, the wear resistance of the product is improved, and meanwhile, the added pyrophyllite is beneficial to perfecting the structure of spodumene, the corrosion resistance and the thermal stability of the ceramic glaze prepared by the invention are improved, and on the other hand, the surface roughness of the ceramic product prepared by the ceramic glaze is reduced, so that pollutants lose accumulation space, and the pollution resistance of the ceramic product is effectively improved.

4. When the antifouling antibacterial material is prepared, capsaicin, ginger powder and the like are used for replacing traditional substances such as nano titanium dioxide, nano silicon dioxide and the like, so that the antifouling antibacterial ceramic prepared by using the antifouling ceramic glaze is more environment-friendly, healthier and safer. The antifouling and antibacterial material of the invention adds the graphene oxide while adding the betaine, the two react to generate amide groups, and simultaneously hydrogen bonds are formed between the graphene oxide layers, so that the structures of the graphene oxide layers are loose and porous, the adsorption performance of the graphene oxide is enhanced, the graphene oxide/dodecyl betaine composite material has enhanced water molecule attracting capacity and good wettability due to the generation of the amide groups, and the ceramic product added with the antifouling and antibacterial material of the invention is easy to spread on the surface of the ceramic product when removing oily pollutants, therefore, water is easy to be immersed between the interfaces of the ceramic and oil drops, and the oil stains adhered on the surface of the ceramic product can be rapidly contacted with the oily pollutants in a short time under the buoyancy action of the water, so that the oily pollutants are fully emulsified and replaced into solution or air from the surface of the ceramic product, the aim of quick cleaning and antifouling is achieved, and the function of killing bacteria and fungi by the graphene oxide is exerted. And capsaicin and ginger both have remarkable sterilization and antifouling effects, and the antibacterial and antifouling properties of the ceramic produced by the antifouling and antibacterial ceramic glaze material prepared by the invention can be better enhanced.

When the ratio of the graphene oxide to the dodecyl betaine is 2.5:2.4, the content of the generated graphene oxide/betaine compound is highest, and the compound is dissolved in an aqueous solution, so that the compound has no obvious large particles, is best in dissolution, is best in dispersibility, and is most stable in property; however, when the ratio of graphene oxide to dodecyl betaine is greater than 2.5:2.4, the amount of graphene oxide is excessive, and the excessive graphene oxide hinders the formation of a graphene oxide/betaine complex due to the large steric hindrance of graphene oxide, so that the content of the complex is reduced, and the dispersibility and stability in an aqueous solution are reduced, and when the ratio of graphene oxide to dodecyl betaine is less than 2.5:2.4, the excessive dodecyl betaine is excessive, and the excessive dodecyl betaine is easily attached to the surface of a ceramic product, so that chemical substance residues are caused, and the health of the ceramic product is impaired after long-term use.

In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below.

Detailed Description

The following is a detailed description of embodiments of the invention, but the invention can be implemented in many different ways, as defined and covered by the claims.