CN101274858A - A self-cleaning sanitary ware glaze with hydrophobic properties and preparation method thereof - Google Patents

Abstract

The invention relates to a self-cleaning sanitary ware glaze with hydrophobic property and a preparation method thereof. The self-cleaning sanitary ware graze comprises ground graze and cover glaze and is characterized in that: the cover glaze is added with fluoride and titanium oxide; refinement is done to the grain size of the glaze material which is burned at a time under the temperature of 1150 to 1300 DEG C, thus obtaining the self-cleaning sanitary ware glaze. The self-cleaning sanitary ware glaze of the invention has the advantage of ensuring the prepared sanitary ware has lucent and clean surfaces and lasting self-clean effect and the surfaces of the sanitary ware are easily cleaned with stain resistant.

Description

A self-cleaning sanitary ware glaze with hydrophobic properties and preparation method thereof

technical field

The invention relates to a porcelain or stoneware sanitary ware glaze, in particular to a self-cleaning sanitary ware glaze with hydrophobic function and a preparation method thereof.

Background technique

Sanitary ware is widely used in daily life due to its beauty, practicality and other advantages. Although the glaze layer on the surface of the sanitary ware is quite dense and smooth, due to the limitation of the production process, there are still tiny pinholes and unevenness on the surface, which makes it contact with some pollutants during use, such as urine and urine. , Scale, urine scale, soap foam, fatty acid, amino acid, etc., under the action of various physical or chemical forces such as van der Waals force, capillary force, hydrogen bond, etc., are easy to accumulate on the unevenness of the surface of the sanitary ware or enter the micropores, resulting in sanitary ware pollution. The pollution on the surface of sanitary ware not only affects the appearance, but also increases the difficulty of cleaning, and the detergent used in cleaning will cause environmental pollution. At the same time, these pollutants will also lead to the proliferation of microorganisms such as bacteria on the surface of sanitary ware, thereby affecting people's health.

In 1805, Young first proposed that the problem of contact angle can be treated as the force balance of a liquid droplet on a plane solid under the interfacial tension of three phases. As the tangent of the gas-liquid interface, the angle between the tangent and the solid-liquid boundary is the contact angle, expressed in θ. If the solid is lyophilic, the liquid's contact angle θ<90°; if the solid is lyophobic, the liquid's contact angle θ>90°. By the following equation:

r _SA =r _SL +r _LA cosθ (equation 1)

cosθ=(r _SA -r _SL )/r _LA (Equation 2)

r _SA , r _SL and r _LA in Equation 1 and Equation 2 represent the interfacial tension of solid/gas, solid/liquid, and liquid/gas interfaces, respectively. From the definition of energy, r _SA , r _SL and r _LA represent solid surface energy, solid-liquid interface energy and liquid surface energy, respectively. That is, the hydrophobic surface with θ>90° can be obtained when r _SA <r _SL .

Therefore, the hydrophobic property can be mainly achieved by reducing the solid surface energy or increasing the solid-liquid interface energy. In addition, for rough surfaces, it can also be achieved by obtaining micro-nano-combined micro-roughness.

However, from practical considerations, most of the pollutants in the field of sanitary ware (such as sewage, urine, etc.) are liquid, and their liquid surface energy and solid-liquid interface energy are fixed and cannot be changed. To obtain a glazed surface with a certain roughness, Its process conditions are limited and will affect the quality of the glaze. Therefore, in order to obtain a sanitary ware glaze with hydrophobic properties, it is necessary to start with reducing the surface energy of the glaze.

In recent years, domestic and foreign sanitary ware manufacturers have mostly applied organic film layers (main materials are fluororesin and silicone resin) on the surface of sanitary ware in terms of hydrophobic and antifouling research to reduce the surface energy of the glaze to achieve hydrophobic treatment. China Patent CN101092289 reports that a super-hydrophobic rough surface material made of core-shell fluoropolymer can realize the transition between the free rolling state and the adhesion state of water droplets on the same surface. Although this process achieves a hydrophobic effect and improves the antifouling performance to a certain extent, due to the low synthesis temperature, the film layer is easy to fall off and the wear resistance is poor.

Contents of the invention

The technical problem to be solved by the present invention is to provide a sanitary ware glaze with good hydrophobic function and wear-resistant effect and a preparation method thereof.

The technical solution of the present invention is: a self-cleaning sanitary ware glaze with hydrophobic properties, comprising a first opaque glaze layer and a second transparent glaze layer formed on the opaque glaze layer, characterized in that:

The composition of the first layer of opaque glaze is as follows: 25-45% of quartz, 15-30% of potassium feldspar, 1-6% of aluminum oxide, 5-15% of Suzhou soil, 8-20% of calcite, white cloud Stone 2-8%, zinc oxide 1-8%, frit 1-5%, zirconium silicate 8-15%;

The composition of the second layer of transparent glaze is by weight percentage: 25-60% of quartz, 15-35% of potassium feldspar, 5-15% of Suzhou soil, 8-18% of calcite, 2-6% of dolomite, and 2-2% of zinc oxide. 10%, frit 2-10%, fluoride 1-10%; titanium oxide 1-5%;

The chemical weight percentage composition of the above frit is: KNaO 2-5%, CaO 4-8%, ZnO 4-8%, Al ₂ O ₃ 5-8%, B ₂ O ₃ 6-10%, SiO ₂ 50- 55%, ZrO ₂ 8-14%.

The fluoride refers to one of Na ₃ AlF ₆ , Na ₂ SiF ₆ , K ₂ SiF ₆ , BaF ₂ , CaF ₂ , MgF ₂ , SrF ₂ , CeF ₃ or a mixture of any of them; preferably Na ₃ AlF ₆ or Na ₂ SiF ₆ or their mixtures.

The preparation method of the present invention is:

(1) According to the raw material composition of the first layer of opaque glaze and the second layer of transparent glaze, respectively prepare glaze slurry with particle diameter D ₅₀ ≤ 10 μm and D ₅₀ ≤ 6 μm;

(2) Spray the opaque glaze slurry evenly on the ceramic biscuit, and form an opaque glaze layer with a thickness of 0.1-0.7mm after drying;

(3) Spray the transparent glaze slurry evenly on the opaque glaze layer, and form a transparent glaze layer with a thickness of 0.1-0.5mm after drying;

(4) Burn at 1150-1300°C and keep warm for 20-40min to obtain the product.

The preparation method of the invention is simple, the source of raw materials is abundant and the price is low. The present invention introduces fluoride and titanium oxide into the second layer of transparent glaze, which can effectively reduce the surface energy of the glaze, endow the glaze with good hydrophobicity and self-cleaning function, and make it have a permanent self-cleaning effect.

Detailed ways

Embodiment 1-6:

Prepare the raw materials according to the composition in Table 1-3, and process parameters in Table 4. After crushing, mixing ball milling, sieving, spraying the first layer of opaque glaze, drying, spraying the second layer of transparent glaze, drying, and firing to obtain the hydrophobic performance Self-cleaning sanitary ware glaze.

Table 1 The composition of opacified glaze material formula (mass fraction%)

raw material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Quartz 40 32 34 36 32 40 Potassium feldspar 16 twenty two 20 18 18 16 Aluminum oxide 2 3 3 4 3 2 Suzhou Soil 6 7 8 6 6 4 Calcite 13 14 14 13 15 15 Dolomite 3 3 4 4 5 5 Zinc oxide 6 4 3 3 4 2 frit 4 4 3 4 5 6 Zirconium silicate 10 11 11 12 12 10

Table 2 Transparent glaze material formula composition (mass fraction%)

raw material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Quartz 40 37 34 44 38 32 Potassium feldspar 18 20 twenty two 18 19 twenty three Suzhou Soil 7 8 6 6 7 8 Calcite 13 13 13 12 14 12 Dolomite 6 5 4 4 5 6 Zinc oxide 6 4 3 4 6 3 frit 4 8 6 8 4 6 Na ₂ SiF ₆ 1 2 8 0 2 9 Na ₃ AlF ₆ 0 2 1 2 4 0 Titanium oxide 5 1 3 2 5 1

Table 3 Chemical composition of frit glaze (mass fraction%)

raw material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 KNaO 2 3 4 5 2 4 CaO 4 6 8 6 6 4 ZnO 8 6 4 8 4 6 Al ₂ O ₃ 5 6 6 8 8 5 B ₂ O ₃ 6 8 10 6 8 6 ZnO 6 4 8 4 8 8 SiO ₂ 55 55 50 52 50 55 _ZrO2 14 12 10 11 14 12

Table 4 Preparation conditions and performance test results

Claims (3)

1, a kind of automatically cleaning sanitary ware glaze with hydrophobic performance comprises the first layer opaque glaze layer, and the second layer transparent layer that forms on the opaque glaze layer, it is characterized in that:

The composition of the first layer opaque glaze is by weight percentage: quartzy 25-45%, potassium felspar sand 15-30%, aluminium sesquioxide 1-6%, Suzhou soil 5-15%, calcite 8-20%, rhombspar 2-8%, zinc oxide 1-8%, frit 1-5%, zirconium silicate 8-15%;

The composition of second layer transparent is by weight percentage: quartzy 25-60%, potassium felspar sand 15-35%, Suzhou soil 5-15%, calcite 8-18%, rhombspar 2-6%, zinc oxide 2-10%, frit 2-10%, fluorochemical 1-10%; Titanium oxide 1%-5%;

The chemical weight percentage composition of above-mentioned frit is: KNaO 2-5%, GaO 4-8%, ZnO 4-8%, Al ₂O ₃5-8%, B ₂O ₃6-10%, SiO ₂50-55%, ZrO ₂8-14%.

2, the automatically cleaning sanitary ware glaze with hydrophobic performance according to claim 1, it is characterized in that: described fluorochemical is Na ₃AlF ₆Or Na ₂SiF ₆Or Na ₃AlF ₆And Na ₂SiF ₆Mixture.

3, the described method with automatically cleaning sanitary ware glaze of hydrophobic performance of preparation claim 1 is characterized in that successively as follows:

(1), prepares particle diameter D respectively by the first layer opaque glaze and second layer transparent raw material composition ₅₀≤ 10 μ m and D ₅₀The glaze slip of≤6 μ m;

(2), the opaque glaze slurries are sprayed uniformly on biscuit of ceramics, to form thickness be the opaque glaze layer of 0.1-0.7mm in the oven dry back;

(3), the transparent slurries are sprayed uniformly on the opaque glaze layer, to form thickness be the transparent layer of 0.1-0.5mm in dry back;

(4), under 1150-1300 ℃, insulation 20-40min condition, burn till the acquisition product.