1. A satin glaze is characterized in that the chemical composition of the satin glaze comprises: by mass percent, SiO₂：35.0～37.0%、Al₂O₃：1.0～2.0%、TiO₂：10.0～11.0%、CaO：9.0～10.0%、MgO：1.5～3.0%、Na₂O: 3.5-4.5%, ZnO: 28.0-33.0%, loss on ignition: 4.5 to 6.5 percent.

2. The satin glaze according to claim 1, which generates crystal grains having a diameter of 0.1 to 0.5mm under firing conditions.

3. The satin glaze according to claim 1 or 2, which produces crystal flowers having a main phase of zinc silicate after firing.

4. The satin glaze according to any one of claims 1 to 3, wherein the raw material composition of the satin glaze comprises: by mass percentage, 28-45% of glass powder, 2-5% of kaolin, 10-16% of calcite, 10-15% of quartz, 10-15% of titanium dioxide, 30-40% of zinc oxide and 2-6% of calcined talc.

5. The satin glaze according to claim 4, wherein the chemical composition of the glass powder comprises: by mass percent, SiO₂：68.0～73.0%、Al₂O₃：1.0～2.0%、Fe₂O₃：0.06～0.36%、TiO₂：0.06～0.36%、CaO：8.0～9.0%、MgO：3.5～4.5%、K₂O：0.1～0.3%、Na₂O: 13.0-14.0%, loss on ignition: 0.1 to 0.5 percent.

6. The satin glaze according to any one of claims 1 to 5, wherein the chemical composition of the satin glaze further comprises: in mass percent, K₂O：0.1～0.3%。

7. A preparation method of a three-dimensional crystal-pattern decorative satin glaze ceramic plate is characterized by comprising the following steps:

applying base coat on the surface of the plate blank and carrying out ink-jet printing on a design pattern;

applying the satin glaze according to any one of claims 1 to 6 on a slab after ink-jet printing of a design pattern;

and drying and firing the blank subjected to the satin glaze.

8. The preparation method according to claim 7, wherein the satin glaze has a specific gravity of 1.82 to 1.88g/cm³The glazing amount is 400-550 g/m²。

9. The production method according to claim 7 or 8, wherein the maximum firing temperature is 1180 to 1220 ℃ and the firing period is 60 to 120 minutes.

10. The stereoscopic crystal flower decorative satin glaze ceramic plate obtained by the preparation method according to any one of claims 7 to 9, wherein the gloss of the satin glaze is 10 to 30 °.

Background

The satin glaze is popular with consumers due to soft surface glossiness, exquisite texture and high wear resistance. At present, the satin glaze on the market is usually a high-aluminum system, and the glaze material causes reaction among ions in the components of the satin glaze due to the characteristic of high-temperature viscosity, so that crystals are difficult to reach a saturated state and are separated out, and the crystal decoration effect of the glaze surface is single and deficient.

Disclosure of Invention

In a first aspect, the present invention provides a satin glaze. The chemical composition of the satin glaze comprises: by mass percent, SiO₂：35.0～37.0％、Al₂O₃：1.0～2.0％、TiO₂：10.0～11.0％、CaO：9.0～10.0％、MgO：1.5～3.0％、Na₂O: 3.5-4.5%, ZnO: 28.0-33.0%, loss on ignition: 4.5 to 6.5 percent.

The content of alumina in the chemical composition of the satin glaze is kept between 1.0 and 2.0 percent, so that the phenomenon that excessive alumina has great influence on the high-temperature viscosity of the glaze, the alumina reacts with sodium oxide, silicon dioxide and the like to generate anorthite crystals can be avoided, and zinc silicate (Zn) is inhibited₂SiO₄) And (5) growing crystals. The content of zinc oxide in the satin glaze is preferably 28.0-33.0%. The zinc oxide in the above content can make the glaze layer have a large amount of Zn²⁺With SiO₂Reaction to form Zn₂SiO₄And (4) crystals. And proper amount of CaO and MgO can reduce the firing temperature of the satin glaze, is beneficial to crystallization of zinc silicate crystals and ensures that the glaze surface has exquisite and soft texture. Furthermore, a suitable content of Na₂O can also reduce the high temperature viscosity of the satin glaze and promote the silicic acidAnd (4) separating out zinc crystals.

Preferably, the chemical composition of the satin glaze further includes: in mass percent, K₂O: 0.1 to 0.3 percent. The sodium metal element is more active than the potassium metal element, and the content of the potassium oxide can be controlled to obtain lower high-temperature viscosity of the glaze, thereby being beneficial to the formation of crystal flowers.

Preferably, the satin glaze generates crystal flowers with the diameter of 0.1-0.5 mm under the firing condition.

Preferably, the satin glaze generates crystal flowers with zinc silicate as a main phase after firing.

Preferably, the raw material composition of the satin glaze comprises: by mass percentage, 28-45% of glass powder, 2-5% of kaolin, 10-16% of calcite, 10-15% of quartz, 10-15% of titanium dioxide, 30-40% of zinc oxide and 2-6% of calcined talc.

Preferably, the chemical composition of the glass powder comprises: by mass percent, SiO₂：68.0～73.0％、Al₂O₃：1.0～2.0％、Fe₂O₃：0.06～0.36％、TiO₂：0.06～0.36％、CaO：8.0～9.0％、MgO：3.5～4.5％、K₂O：0.1～0.3％、Na₂O: 13.0-14.0%, loss on ignition: 0.1 to 0.5 percent.

In a second aspect, the invention provides a preparation method of a three-dimensional crystal-pattern decorative satin glazed ceramic plate. The preparation method comprises the following steps: applying base coat on the surface of the plate blank and carrying out ink-jet printing on a design pattern; applying the satin glaze of any one of the above on a plate blank after ink-jet printing of a design pattern; and drying and firing the plate blank subjected to the stereoscopic crystal pattern satin glaze.

Preferably, the specific gravity of the satin glaze is 1.82-1.88 g/cm³The glazing amount is 400-550 g/m²。

Preferably, the maximum firing temperature is 1180-1220 ℃, and the firing period is 60-120 minutes.

In a third aspect, the invention provides a three-dimensional crystal flower decorative satin glaze ceramic plate obtained by the preparation method. The glossiness of the satin glaze surface is 10-30 degrees.

Drawings

FIG. 1 is a flow chart of a process for preparing a three-dimensional crystal-patterned decorative satin glazed ceramic plate;

FIG. 2 is a plate surface effect diagram of a three-dimensional crystal-patterned decorative satin-glazed ceramic plate according to example 1;

FIG. 3 is a satin glaze effect drawing under a magnifying glass of 100 times of the stereoscopic crystal flower decorative satin glaze ceramic plate of example 1;

FIG. 4 is a plate surface XRD pattern of the three-dimensional crystal-patterned decorative satin-glazed ceramic plate of example 1.

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 means a mass percentage.

The satin glaze, the three-dimensional crystal pattern decorated satin glaze ceramic plate and the preparation method thereof according to the present invention are exemplarily described below.

Pressing into a plate blank by using a ceramic base material. The composition of the ceramic base material is not limited, and the ceramic base material can be common ceramic base material. As an example, the chemical composition of the ceramic base material may include, in mass percent, loss on ignition: 5.0 to 6.0% of SiO₂：61～66％、Al₂O₃：21～24％、Fe₂O₃：0.5～1.5％、TiO₂：0.1～0.5％、CaO：0.1～0.5％、MgO：0.3～0.8％、K₂O：2.0～3.0％、Na₂O：2.5～3.5％。

The mat is dried. Drying in a drying kiln may be used. The drying time can be 1-1.5 h, and the moisture of the dried plate blank is controlled within 0.3-0.5 wt%.

And applying base coat on the surface of the dried plate blank. The primary purpose of the undercoating is to hide green body imperfections. In some embodiments, the chemical composition of the ground glaze may include, in mass percent: SiO 2₂：55～60％、Al₂O₃：21～24％、Fe₂O₃：0.16～0.46％、TiO₂：0.15～0.25％、CaO：0.1～0.3％、MgO：0.1～0.3％、K₂O：4.0～5.0％、Na₂O：2.0～3.0％、ZrO₂: 6.0-10.0%, loss on ignition: 3.0 to 4.0 percent.

The ground coat can be applied by spraying glaze. For example, the specific gravity of the ground coat is 1.40 to 1.45g/cm³The glazing amount is 500-650 g/m²。

And printing a pattern on the base plate blank after the base coat is applied by ink jet. The color and pattern of the ink jet printed pattern are adaptively changed depending on the design effect.

And applying satin glaze on the blank subjected to the ink-jet printing. The satin glaze is a high-zinc and high-titanium system. In some embodiments, the chemical composition of the satin glaze may include: SiO in mass percent₂：35.0～37.0％、Al₂O₃：1.0～2.0％、TiO₂：10.0～11.0％、CaO：9.0～10.0％、MgO：1.5～3.0％、Na₂O: 3.5-4.5%, ZnO: 28.0-33.0%, loss on ignition: 4.5 to 6.5 percent. The satin glaze needs to reasonably control the content of CaO, MgO and the like. Along with the increase of the CaO content, the high-temperature viscosity of the glaze material is reduced, a large amount of large crystal grains are separated out from the glaze layer, but along with the continuous increase of the CaO content, the crystal grains in the glaze layer are gradually melted until the crystal grains completely disappear, and at the moment, the glaze material is a low-temperature transparent glaze system. If the content of MgO is too low, the texture of the glaze surface is deteriorated, because large crystal flowers are locally precipitated on the glaze layer and the glaze layer presents a low-temperature bright state at the positions without the crystal flowers; with the continuous rise of the MgO content, the high-temperature viscosity of the glaze is further reduced, a large number of small crystal flowers are separated out from the glaze layer, the firing range is widened, the texture of the glaze layer is fine, but the size of the crystal flowers is reduced. The high titanium dioxide content mainly promotes the precipitation of zinc silicate crystal flowers.

The currently known satin glaze mainly adopts a high-aluminum high-calcium system. For example, the chemical composition of a high-aluminum high-calcium satin glaze may include: by mass percent, SiO₂：45.0～50.0％、Al₂O₃：18.0～22.0％、Fe₂O₃：0.06～0.36％、TiO₂：0.1～0.3％、CaO：8.5～10.5％、MgO：3.0～4.0％、K₂O：2.5～3.5％、Na₂O: 2.0-3.0%, ZnO: 3.0-4.0%, loss on ignition: 6.5 to 7.5 percent. The glaze has low high-temperature viscosityThe main crystallization substance reaches a saturated state, which is beneficial to the crystallization of crystal flowers in the glaze layer. The satin glaze with the composition has high-temperature viscosity, various ions in the components of the satin glaze react with each other, and crystals are difficult to reach a saturated state and are separated out. Furthermore, SiO in the satin glaze₂、Al₂O₃The content is higher, the influence on the high-temperature viscosity of the glaze is large, and even no crystal species which can reach saturation and is separated out exists in the glaze.

The raw material composition of the satin glaze can comprise: the glass powder comprises the following components in percentage by mass: 28-45% of kaolin: 2-5% of calcite: 10-16% of quartz powder: 10-15% and titanium dioxide: 10-15%, zinc oxide: 30-40%, and calcined talc: 2-6%. Calcite, burnt talc act as matting agent. The higher the glass frit content, the higher the gloss. The glossiness of the satin glaze surface can be better controlled by controlling the contents of the glass powder, the calcite and the calcined talc. In some embodiments, the chemical composition of the glass frit may include: by mass percent, SiO₂：68.0～73.0％、Al₂O₃：1.0～2.0％、Fe₂O₃：0.06～0.36％、TiO₂：0.06～0.36％、CaO：8.0～9.0％、MgO：3.5～4.5％、K₂O：0.1～0.3％、Na₂O: 13.0-14.0%, loss on ignition: 0.1 to 0.5 percent.

When preparing the satin glaze, weighing the raw materials according to the raw material composition of the satin glaze and ball-milling. In the ball milling process, milling balls: drying glaze: the mass ratio of water is 1: 1: 0.45. ball-milling until the fineness of the glaze slip reaches 325 meshes and the residual weight is 0.4-0.62 percent. Then discharging slurry and ageing to obtain the satin glaze.

The satin glaze can be applied by spraying glaze. The glaze surface flatness of the sprayed glaze is better than that of the sprayed glaze. In some embodiments, the satin glaze has a specific gravity of 1.82 to 1.88g/cm³The glazing amount is 400-550 g/m². Controlling the glazing parameters in the above range can better control the crystallization, glaze texture and glossiness of the board surface. The glazing amount is too small, the number of small crystal flowers separated out from the glaze surface is limited, the glossiness of the glaze surface is higher, and the texture of satin glaze cannot be realized; if the glazing amount is too much, the crystal flowers are re-melted and the glaze surface is smoothThe glossiness is higher, does not present satin glaze feel. Certainly, the glaze spraying mode can be selected, but the glaze applying parameters need to be adjusted correspondingly to ensure that the solid content of the glaze is consistent with that of the glaze spraying.

And drying the blank subjected to the satin glaze. The drying can be carried out by electric drying or hot air drying oven drying. The drying temperature can be 100-150 ℃, and the moisture of the dried plate blank is controlled within 0.9 wt%.

And (5) firing. The highest firing temperature can be 1180-1220 ℃, and the firing period can be 60-120 minutes. The satin glaze after firing has a crystal pattern with a main phase of zinc silicate (fig. 4).

According to the invention, by adjusting and optimizing the formula of the satin glaze, the glaze surface has the gloss texture of the satin glaze and can also separate out a large number of crystal flowers in the glaze layer, the crystal flowers are mutually interwoven, the positions where the crystal flowers exist are soft light effects, and the positions of small lines (positions without crystal flowers) where a small number of crystal flowers are connected are bright light effects. The separated small crystal flowers can reduce the glossiness of the glaze, and the positions with small local small crystal flowers are relatively high in glossiness, so that the texture effect of bright and matte combination is formed, and the three-dimensional decoration of the glaze is facilitated. In addition, the satin glaze can also play a role in protecting the glaze, prevent patterns from being worn, and prevent the additionally applied protecting glaze from influencing the crystallization of the board surface, the texture of the glaze surface, the glossiness and other board surface defects caused by the extra protecting glaze. In addition, the three-dimensional crystal flower decorative satin glaze ceramic plate has rich three-dimensional decorative effect while having soft glossiness and better glaze texture.

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.

Example 1

(1) Dry-pressing the ceramic base material to form a plate blank;

(2) drying the plate blank for 1-1.5 h, and controlling the water content of the dried plate blank within 0.3-0.5 wt%;

(3) spraying a ground coat on the surface of the plate blank, wherein the specific gravity of the ground coat is 1.40-1.45 g/cm³The glazing amount is 400-550 g/m²；

(4) Printing a design pattern on the surface of the plate blank after spraying the ground coat in an ink-jet manner;

(5) applying satin glaze on the surface of the plate blank after ink-jet printing of the design pattern, wherein the specific gravity of the satin glaze is 1.82-1.88 g/cm³The glazing amount is 400-550 g/m²(ii) a The raw material composition of the satin glaze comprises: the glass powder comprises the following components in percentage by mass: 30.7%, kaolin: 2.6%, calcite: 12.3%, quartz: 11.5%, titanium dioxide: 10.4%, zinc oxide: 30.7%, calcined talc: 1.8 percent; the chemical composition of the satin glaze comprises: by mass percent, SiO₂：35.85％、Al₂O₃：1.31％、Fe₂O₃：0.07％、TiO₂：10.36％、CaO：9.55％、MgO：1.80％、K₂O：0.13％、Na₂O: 4.05%, ZnO: 30.39%, loss on ignition: 5.54 percent;

(6) drying the plate blank after the satin glaze is applied; the drying temperature is 100-150 ℃, and the moisture of the dried plate blank is controlled within 0.9 wt%;

(7) and (4) sintering, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-120 minutes.

(8) And (5) edging, grading, packaging and warehousing.

Fig. 2 is a plate surface effect diagram of a three-dimensional crystal-pattern decorative satin glazed ceramic plate. A large number of crystal flowers (with the diameter of 0.1-0.5 mm) are separated out from the glaze layer, the crystal flowers are mutually interwoven, the positions of the crystal flowers are soft, and the positions of small lines (without the crystal flowers) where a small number of crystal flowers are connected are bright, so that a bright and matte combined texture effect is formed, and the three-dimensional decoration of the glaze is facilitated and the fine texture of the glaze is improved.

Fig. 3 is a satin glaze effect picture of a solid crystal flower decoration satin glaze ceramic plate under a magnifying glass of 100 times. Most board surfaces have more fine needle-shaped crystal flowers (the diameter is 0.1-0.5 mm), and a large number of continuous and staggered crystal flowers exist locally, so that a good decoration effect is achieved, and the texture of the board surfaces is not influenced.

Example 2

Essentially the same as example 1, except that: the raw materials of the satin glaze comprise: the glass powder comprises the following components in percentage by mass: 28.1%, kaolin: 2.6%, calcite: 10.3%, quartz: 11.5%, titanium dioxide: 11.0%, zinc oxide: 31.5%, calcined talc: 5.0 percent; the chemical composition of the satin glaze comprises: by mass percent, SiO₂：36.01％、Al₂O₃：1.28％、Fe₂O₃：0.06％、TiO₂：10.96％、CaO：8.30％、MgO：2.74％、K₂O：0.13％、Na₂O: 3.70%, ZnO: 31.19%, loss on ignition: 4.71 percent.

Example 3

Essentially the same as example 1, except that: the raw materials of the satin glaze comprise: by mass percentage, 30.1 percent of glass powder, 2.6 percent of kaolin, 12.3 percent of calcite, 11.5 percent of quartz, 10.4 percent of titanium dioxide, 30.1 percent of zinc oxide and 3.0 percent of calcined talc; the chemical composition of the satin glaze comprises: by mass percent, SiO₂：36.18％、Al₂O₃：1.30％、Fe₂O₃：0.07％、TiO₂：10.36％、CaO：9.53％、MgO：2.17％、K₂O：0.13％、Na₂O: 3.97%, ZnO: 29.80%, loss on ignition: 5.55 percent.

Comparative example 1

Essentially the same as example 1, except that: the raw materials of the satin glaze comprise: by mass percentage, 31.1 percent of glass powder, 2.6 percent of kaolin, 12.3 percent of calcite, 11.5 percent of quartz, 11.0 percent of titanium dioxide and 31.5 percent of zinc oxide. After the sintering, a plurality of white crystal patterns with the diameter of about 0.3-0.5 mm (large size) appear on the board surface, and the glaze surface gloss is 79 degrees. This is because the introduction of the burnt talc lowers the high temperature viscosity of the glaze, so the formulation of this comparative example has a relatively high temperature viscosity, promoting the growth of large-size crystal grains.

Comparative example 2

Essentially the same as example 1, except that: the raw materials of the satin glaze comprise: by mass percentage, 45.0 percent of glass powder, 2.6 percent of kaolin, 12.3 percent of calcite, 10.0 percent of titanium dioxide and 30.1 percent of zinc oxide; the chemical composition of the satin glaze comprises: by mass percent, SiO₂：33.59％、Al₂O₃：1.50％、Fe₂O₃：0.08％、TiO₂：9.97％、CaO：10.76％、MgO：1.77％、K₂O：0.17％、Na₂O: 5.93%, ZnO: 29.80%, loss on ignition: 5.57 percent. The satin glaze of the formula does not generate any crystal flower under the same firing condition, and the glaze glossiness is 104.5 degrees. The invention mainly removes quartz and burning talc, which reduces the sintering temperature of glaze, lowers the high temperature viscosity, and dissolves crystal patterns separated out from glaze surface again.