CN115650587A - Reflective heat-insulation glaze, reflective heat-insulation ceramic tile and preparation method and application thereof - Google Patents

Abstract

The invention relates to the field of ceramic tiles, in particular to a reflective heat-insulating glaze, a reflective heat-insulating ceramic tile, and a preparation method and application thereof. The preparation method of the reflective heat-insulating glaze comprises the following steps: titanium frit, zirconium white frit, zirconia powder, titanium dioxide and activated alumina powder; the reflective heat-insulating glaze contains TiO ₂ The mass percent of the TiO-based reflective heat-insulating glaze is 8-15%, and the mass percent of the TiO in the reflective heat-insulating glaze is more than or equal to 4% ₂ From titanium frit; the reflecting heat-insulating glaze contains ZrO ₂ The mass percent of the ZrO is more than or equal to 2 percent, and the mass percent of the ZrO in the reflective heat-insulating glaze is more than or equal to 0.5 percent ₂ From zirconium white frit; in the preparation of the raw materials, the median particle size of the zirconia powder is 0.4-0.7 μm. The reflective heat-insulating glaze enables the ceramic tile to have high sunlight reflectance.

Description

Reflective heat-insulation glaze, reflective heat-insulation ceramic tile and preparation method and application thereof

Technical Field

The invention relates to the field of ceramic tiles, in particular to a reflective heat-insulation glaze material, a reflective heat-insulation ceramic tile, and a preparation method and application thereof.

Background

In summer, the building is strongly irradiated by sunlight, and the indoor temperature is higher, so that the energy consumption of air conditioner refrigeration is large. The solar reflection heat insulation material applied to the peripheral roof and the wall surface of the building can reflect more solar rays, and reduce the temperature of the surface of the building and the ambient air so as to realize the passive cooling of the building, thereby reducing the power consumption of refrigeration equipment and achieving the effects of energy conservation and environmental protection. At present, a plurality of materials for resisting solar heat radiation are applied, such as energy-saving glass curtain walls, phase change energy storage wall materials, reflective heat insulation coatings and the like. The energy-saving glass curtain wall and the phase-change energy storage wall are rarely used at the periphery of the civil residential building due to complex production and manufacturing process, high installation difficulty, high cost and the like. The reflective heat-insulating coating is used more, but has short service life and easy aging and falling off, and is generally required to be recoated after being used for several years, thereby bringing environmental pollution and interfering with daily work and life.

The ceramic tile has the first impression of durability, particularly compact surface structure of the glazed tile, cleaner appearance of a building after being washed by rainwater compared with a coating, excellent weather resistance, service life, easy cleaning performance and strength. The ceramic tiles with high reflection and heat insulation performance are paved on the periphery and the roof of the building, so that the passive cooling of the building is realized, the use strength of an air conditioner in summer is reduced, and the effects of building energy conservation and consumption reduction are achieved. The sunlight reflection ratio of the existing light-colored ceramic tiles for the periphery of buildings is lower and cannot reach the sunlight reflection ratio required by GB/T25261-2018 for reflective heat-insulating coatings for buildings.

Disclosure of Invention

In view of this, there is a need to provide a reflective insulating glaze which can be used as a material for the ground coat layer of ceramic tiles, so that the ceramic tiles have a high solar reflectance.

In addition, a reflective heat insulation ceramic tile, a preparation method and application thereof are also needed to be provided.

A reflective heat-insulating glaze comprises the following raw materials: titanium frit, zirconium white frit, zirconia powder, titanium dioxide and activated alumina powder;

the reflective heat-insulating glaze contains TiO ₂ The mass percent of the reflective heat-insulation glaze is 8% -15%, and the mass percent of TiO in the reflective heat-insulation glaze is more than or equal to 4% ₂ From the titanium frit;

the reflective heat-insulating glaze contains ZrO ₂ The mass percent of the ZrO is more than or equal to 2 percent, and the mass percent of the ZrO in the reflective heat-insulating glaze is more than or equal to 0.5 percent ₂ From the zirconium white frit;

in the preparation raw materials, the median particle size of the zirconia powder is 0.4-0.7 μm.

In one embodiment, the reflective insulating glaze comprises the following chemical components in percentage by mass: 50% -60% SiO ₂ 、5%~12% Al ₂ O ₃ 、8%~15% TiO ₂ 、2%~8% ZrO ₂ 、0.5%~2% K ₂ O、0~1% Na ₂ O、0~1% B ₂ O ₃ 、12%~20% CaO、1%~2% MgO、0~2% BaO、0~2% SrO、0~1% ZnO、0~1% P ₂ O ₅ 、0~0.2% Fe ₂ O ₃ And 0~8% loss on ignition.

In one embodiment, the raw materials for preparing the reflective insulating glaze comprise, by mass: 40-60% of titanium frit, 10-20% of zirconium white frit, 10-20% of quartz powder, 0< active alumina powder is less than or equal to 5%, 3-10% of titanium dioxide, 1-5% of zirconia powder, 0~5% of zirconium silicate, 0-15% of calcite, 0-10% of wollastonite, 0~3% of dolomite, 0~3% of barium carbonate, 0~3% of strontium carbonate, 5-10% of kaolin, 0~5% of potassium feldspar, 0~5% of sodium feldspar and 0~5% of calcined talc;

in the preparation raw materials, median particle diameters of the zirconia powder, the quartz powder and the titanium dioxide are respectively 0.4-0.7 μm, 2-4 μm and 0.6-1 μm.

In one embodiment, the chemical composition of the titanium frit comprises, in mass percent: 50% -60% SiO ₂ 、8%~12% TiO ₂ 、4%~6% Al ₂ O ₃ 、0~3% MgO、18%~25% CaO、1%~2% Na ₂ O、1%~3% K ₂ O、0~0.3% Fe ₂ O ₃ 、0~1% P ₂ O ₅ And ignition loss is less than or equal to 0.3 percent;

chemical group of the zirconium white frit according to mass percentageThe method comprises the following steps: 50% -60% SiO ₂ 、2%~5% Al ₂ O ₃ 、2%~5% B ₂ O ₃ 、7%~10% ZrO ₂ 、1%~3% MgO、22%~30% CaO、0.5%~1.5% Na ₂ O、0.5%~1% K ₂ O、2%~5% ZnO、0~0.3% Fe ₂ O ₃ 、0~0.2% TiO ₂ And the ignition loss is less than or equal to 0.3 percent.

The reflective heat-insulation ceramic tile comprises a ceramic body layer, a ground coat layer, a surface coat layer and a pattern layer which are sequentially stacked, wherein the raw materials for preparing the ground coat layer comprise the reflective heat-insulation glaze.

In one embodiment, the thickness of the ground glaze layer is more than or equal to 0.2mm; the thickness of the overglaze layer is 0.05mm to 0.2mm.

In one embodiment, the overglaze layer satisfies at least one of the following conditions:

(1) The chemical composition of the overglaze layer comprises the following components in percentage by mass: 50% -60% SiO ₂ 、5%~10% Al ₂ O ₃ 、0~2% B ₂ O ₃ 、1%~3% Na ₂ O、0~1% K ₂ O、15%~25% CaO、0~2% MgO、0~1% SrO、0~1% BaO、2%~4% ZnO、0~0.3% P ₂ O ₅ 、0~0.2% TiO ₂ 、0~0.3% Fe ₂ O ₃ And 5% -10% loss on ignition;

(2) The overglaze layer is prepared from the following raw materials in percentage by mass: 5% -15% of transparent frit, 20% -40% of albite, 15% -25% of quartz, 12% -24% of calcite, 15% -25% of wollastonite, 0~3% of zinc oxide, 0~2% of barium carbonate, 0~2% of strontium carbonate and 5% -10% of kaolin;

wherein the chemical composition of the transparent frit comprises, by mass: 55% -65% of SiO ₂ 、0~1%Na ₂ O、3%~5% K ₂ O、4%~7% Al ₂ O ₃ 、2%~6% B ₂ O ₃ 、0~2% MgO、10%~18% CaO、6%~10% ZnO、0~3% BaO、0~0.2% P ₂ O ₅ 、0~0.2% TiO ₂ 、0~0.2% Fe ₂ O ₃ And the ignition loss is less than or equal to 0.5 percent.

In one embodiment, the brightness L of the reflective heat-insulation ceramic tile is more than or equal to 90, and the sunlight reflection ratio is more than or equal to L/100-0.15.

A preparation method of a reflective heat-insulation ceramic tile is the reflective heat-insulation ceramic tile, and comprises the following steps:

(1) Preparing the ceramic green body layer;

(2) Applying a ground coat on the surface of the ceramic blank body layer to form the ground coat layer;

(3) Applying a surface glaze on the surface of the ground glaze layer to form the surface glaze layer;

(4) Ink-jet printing is carried out on the surface of the overglaze layer to form the pattern layer;

(5) After the pattern layer is prepared, firing at the firing temperature of 1150-1250 ℃ for 30-80 minutes to obtain a primary finished product of the ceramic tile; edging the primary finished product of the ceramic tile to obtain the reflective heat-insulating ceramic tile;

wherein, in the preparation of the ground glaze layer, the specific gravity of the glaze slip is 1.75g/cm ³ ~1.85g/cm ³ The glazing amount is 500g/m ² ~2500g/m ² ；

In the preparation of the surface glaze layer, the specific gravity of the glaze slip is 1.3g/cm ³ ~1.4g/cm ³ The glazing amount is 150g/m ² ~600g/m ² 。

The reflective heat-insulating ceramic tile is applied to building decoration or building energy conservation.

The preparation raw materials of the reflective heat-insulating glaze comprise: titanium frit, zirconium white frit, zirconia powder, titanium dioxide powder and activated alumina powder (gamma-Al) ₂ O ₃ ) Adjusting TiO introduced by titanium frit in reflective heat-insulating glaze ₂ The mass percent of the zirconia is more than or equal to 4 percent, and ZrO is introduced by the zirconium white clinker ₂ The mass percentage of the titanium sphene, the zirconium silicate, the zirconium oxide and other high-refractive-index crystalline phases with higher content can be separated out from the reflective heat-insulating glaze under the condition of quick firing of a roller kiln by controlling the particle size of the zirconium oxide, so that the glaze layer has higher sunlight reflectance ratio to the sunlight full-wave band.

Drawings

FIG. 1 is a schematic view of one embodiment of a reflective insulation ceramic tile;

FIG. 2 is a process flow diagram of one embodiment of a method for making a reflective insulation ceramic tile;

FIG. 3 is an XRD pattern of the bottom glaze layer in the reflective insulation ceramic tile of example 1;

FIG. 4 is an XRD pattern of the overglaze layer in the reflective insulation ceramic tile of example 1.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Specifically, the reflective insulating glaze of an embodiment is prepared from the following raw materials: titanium frit, zirconium white frit, activated alumina powder (gamma-Al) ₂ O ₃ ) Zirconium oxide powder and titanium dioxide;

the reflective heat-insulating glaze contains TiO ₂ The mass percent of the TiO-based reflective heat-insulating glaze is 8-15%, and the mass percent of the TiO in the reflective heat-insulating glaze is more than or equal to 4% ₂ From titanium frit. Furthermore, the reflective heat-insulating glaze contains TiO ₂ The mass percentage of the component (A) is 9% -13%.

The reflecting heat-insulating glaze contains ZrO ₂ The mass percent of the ZrO is more than or equal to 2 percent, and the mass percent of the ZrO in the reflective heat-insulating glaze is more than or equal to 0.5 percent ₂ From zirconium white frit. Further, the reflective heat-insulating glaze contains ZrO ₂ The mass percentage of the component (A) is 2% -8%. Furthermore, the reflective insulating glaze contains ZrO ₂ The mass percentage of the component (A) is 2% -6%.

In the preparation of the raw materials, the median particle size of the zirconia powder is 0.4-0.7 μm.

At the reflecting partitionIn hot glazes, tiO introduced as titanium frit ₂ The mass percent of the zirconia is more than or equal to 4 percent, and ZrO is introduced by the zirconium white clinker ₂ The mass percentage of the titanium titanite, the zirconium silicate, the zirconium oxide and other high-refractive-index crystalline phases with higher content are separated out from the reflective heat-insulating glaze under the condition of quick firing of the roller kiln, so that the glaze layer has higher sunlight reflection ratio to the full-wave band of sunlight. If the TiO is introduced in the form of a titanium frit ₂ Content less than 4%, zrO introduced by zirconium white frit ₂ Less than 0.5 percent, under the condition of quick firing in a roller kiln, the reflective heat-insulating glaze does not reach the sintering degree, the generated high-refractive-index crystalline phases such as titanium sphene, zirconium silicate, zirconium oxide and the like are low, and TiO introduced in the form of titanium dioxide ₂ The components can not be completely generated into titanium sphene, and rutile or titanium ions enter a glass phase, so that the glaze surface is yellowed, and the reflectivity of the titanium sphene to the sunlight infrared band is low.

In some embodiments, the titanium frit is present in the raw materials for preparation in an amount of 40 to 60% by mass. For example, the titanium frit may be, but is not limited to, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60% by mass or a range consisting of any two of these values. Further, the titanium frit is 45-55% by mass.

In one embodiment, the titanium frit is a commercially available titanium frit for interior wall tiles. Specifically, the chemical composition of the titanium frit comprises, by mass percent: 50% -60% SiO ₂ 、8%~12% TiO ₂ 、4%~6% Al ₂ O ₃ 、0~3% MgO、18%~25% CaO、1%~2% Na ₂ O、1%~3% K ₂ O、0~0.3% Fe ₂ O ₃ 、0~1% P ₂ O ₅ And the ignition loss is less than or equal to 0.3 percent.

In some embodiments, the zirconium white frit is present in the raw materials for preparation in an amount of 10% to 20% by weight. For example, the mass percentage of the zirconium white frit may be, but is not limited to, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or a range consisting of any two of these values. Further, the mass percent of the zirconium white frit is 10% -18%.

In one embodiment, the zirconium white frit is commercially availableThe inner wall brick of (2) is made of zirconium white frit. Specifically, the chemical composition of the zirconium white frit comprises, by mass: 50% -60% SiO ₂ 、2%~5% Al ₂ O ₃ 、2%~5% B ₂ O ₃ 、7%~10% ZrO ₂ 、1%~3% MgO、22%~30% CaO、0.5%~1.5% Na ₂ O、0.5%~1% K ₂ O、2%~5% ZnO、0~0.3% Fe ₂ O ₃ 、0~0.2% TiO ₂ And the ignition loss is less than or equal to 0.3 percent.

The use of commercially available titanium frits and zirconium white frits can reduce costs and process difficulties.

In some embodiments, the zirconia powder has a median particle size of 0.4 μm to 0.7 μm. The zirconia powder raw material with submicron grade high refractive index can be remained in the glaze layer to further improve the reflectance ratio of sunlight visible light wave band, and can improve the high-temperature viscosity of the glaze melt containing zirconium during firing to widen the firing temperature range of the reflective heat-insulating glaze. If the particle size of the zirconia powder is too large, the reflection of the zirconia crystal phase with large particle size to the sunlight visible light wave band is low.

Further, in the preparation raw materials, the mass percent of the zirconia powder is 1-5%. For example, the mass percentage of the zirconia powder may be, but is not limited to, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a range consisting of any two of these values. Further, in the preparation raw materials, the mass percent of the zirconia powder is 2-5%.

In some embodiments, the titanium dioxide is present in the raw materials for preparation in a mass percentage of 3% to 10%. For example, the mass percentage of titanium dioxide may be, but is not limited to, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, or a range consisting of any two of these values. Further, in the preparation raw materials, the mass percent of the titanium dioxide is 3-8%.

Furthermore, the median particle size of the titanium dioxide is 0.6-1 μm. The titanium dioxide with the particle size of 0.6-1 mu m is beneficial to carrying out solid-phase reaction with silicon oxide and calcium oxide in the glaze to produce more titanium sphene crystal phases, and the titanium sphene crystal phases can further improve the sunlight reflectivity performance of the glaze layer. If the particle size of the titanium dioxide is too large, the titanium dioxide with the larger particle size is not beneficial to the reaction for generating the titanium sphene.

The inner wall brick is ceramic brick with sintering temperature below 1100 deg.c and active alumina powder (gamma-Al) added into the material ₂ O ₃ ) The firing temperature of the glaze taking titanium frit and zirconium white frit for interior wall tiles as main raw materials can be increased to 1150-1250 ℃, the firing temperature of the ceramic tile blank is met, and a large amount of high-refractive-index crystal phases can be separated out from the glaze layer, so that the ceramic tile has a high L value, the glaze surface is not yellow, and the glaze layer has a high sunlight reflection ratio, and has a reflection and heat insulation function. If calcined alumina (alpha-Al) ₂ O ₃ ) The introduction of the form can not improve the firing temperature of the ground glaze mainly comprising titanium frit and zirconium white frit, miliaria bubbles appear on the glaze surface when the ground glaze is fired at 1150-1250 ℃, pinholes appear on the glaze surface when a surface glaze layer is applied, so that the glaze surface quality of a product is influenced, meanwhile, the glaze surface is yellow, and the sunlight reflection ratio of the ceramic tile is greatly reduced.

In one example, in preparing the raw materials, activated alumina powder (γ -Al) ₂ O ₃ ) Is 0~5% by mass, excluding 0. For example, activated alumina powder (. Gamma. -Al) ₂ O ₃ ) The mass percentage of (b) may be, but is not limited to, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a range consisting of any two of these values. Further, in the preparation of the raw materials, the mass percent of the active alumina powder is 2-5%.

In some embodiments, the raw materials for preparing the reflective insulating glaze further comprise: and (3) quartz powder.

Furthermore, in the preparation of raw materials, the median particle size of the quartz powder is 2-4 μm. The quartz powder raw material with the particle size of 2-4 microns can be dissolved in a glaze melt at high temperature, the high-temperature viscosity of the glaze melt is improved to separate out finer crystals, titanium sphene separated out from a titanium frit glaze is reduced to be dissolved at high temperature, quartz crystal phase residue is reduced, and the thermal expansion coefficient of a glaze layer is reduced. If the particle size of the quartz powder is too large, the quartz powder with large particle size remains in the glaze layer, so that the thermal expansion coefficient of the glaze layer is larger, and the thermal shock resistance of the reflective heat-insulation ceramic tile is unqualified.

In some embodiments, the mass percentage of the quartz powder in the raw material is 10% -20%. For example, the mass percentage of the silica powder may be, but is not limited to, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or a range including any two of these values. Further, in the preparation raw materials, the mass percent of the quartz powder is 15-20%.

In some embodiments, the raw materials for preparing the reflective insulating glaze further comprise any one or more of kaolin, zirconium silicate, calcite, dolomite, barium carbonate, strontium carbonate, wollastonite, potassium feldspar, albite and calcined talc.

In one embodiment, the raw materials for preparing the reflective insulating glaze comprise, by mass: 40% -60% of titanium frit, 10% -20% of zirconium white frit, 10% -20% of quartz powder and 0<Activated alumina powder (gamma-Al) ₂ O ₃ ) Less than or equal to 5 percent, 3 to 10 percent of titanium dioxide, 1 to 5 percent of zirconia powder, 0~5 percent of zirconium silicate, 0 to 15 percent of calcite, 0 to 10 percent of wollastonite, 0~3 percent of dolomite, 0~3 percent of barium carbonate, 0~3 percent of strontium carbonate, 5 to 10 percent of kaolin, 0~5 percent of potassium feldspar, 0~5 percent of sodium feldspar and 0~5 percent of calcined talc. Wherein the median particle diameters of the zirconia powder, the quartz powder and the titanium dioxide are respectively 0.4-0.7 μm, 2-4 μm and 0.6-1 μm. The titanium frit comprises the following chemical components in percentage by mass: 50% -60% SiO ₂ 、8%~12% TiO ₂ 、4%~6% Al ₂ O ₃ 、0~3% MgO、18%~25% CaO、1%~2% Na ₂ O、1%~3% K ₂ O、0~0.3% Fe ₂ O ₃ 、0~1% P ₂ O ₅ And the ignition loss is less than or equal to 0.3 percent; the zirconium white frit comprises the following chemical components in percentage by mass: 50% -60% SiO ₂ 、2%~5% Al ₂ O ₃ 、2%~5% B ₂ O ₃ 、7%~10% ZrO ₂ 、1%~3% MgO、22%~30% CaO、0.5%~1.5% Na ₂ O、0.5%~1% K ₂ O、2%~5% ZnO、0~0.3% Fe ₂ O ₃ 、0~0.2% TiO ₂ And the ignition loss is less than or equal to 0.3 percent.

Further, the preparation raw materials comprise the following components in percentage by mass: 45% -55% of titanium frit, 10% -18% of zirconium white frit, 15% -20% of quartz powder and 2% -5% of active alumina powder (gamma-Al) ₂ O ₃ ) 3% -8% of titanium dioxide, 2% -5% of zirconia powder, 0~2% of siliconZirconium acid, 3% -8% of calcite, 2% -6% of wollastonite, 0~2% of dolomite, 0~1% of barium carbonate, 0~1% of strontium carbonate, 5% -8% of kaolin, 0~3% of potassium feldspar, 0~3% of albite and 0~3% of calcined talc.

In some embodiments, the reflective insulating frit comprises the following chemical components in percentage by mass: 50% -60% SiO ₂ 、5%~12% Al ₂ O ₃ 、8%~15% TiO ₂ 、2%~8% ZrO ₂ 、0.5%~2% K ₂ O、0~1% Na ₂ O、0~1% B ₂ O ₃ 、12%~20% CaO、1%~2% MgO、0~2% BaO、0~2% SrO、0~1% ZnO、0~1% P ₂ O ₅ 、0~0.2% Fe ₂ O ₃ And 0~8% loss on ignition.

Further, the reflective heat-insulating glaze comprises the following chemical components in percentage by mass: 52% -60% SiO ₂ 、6%~10% Al ₂ O ₃ 、9%~13% TiO ₂ 、2%~6% ZrO ₂ 、0.5%~1.5% K ₂ O、0~1% Na ₂ O、0~1% B ₂ O ₃ 、15%~20% CaO、1%~2% MgO、0~1% BaO、0~1% SrO、0~1% ZnO、0~1% P ₂ O ₅ 、0~0.2% Fe ₂ O ₃ And 2% -6% loss on ignition.

At present, the research and application of ceramic tile products with high sunlight reflectance at home and abroad are in the primary stage, the traditional technology discloses a preparation method of a reflective heat-insulation ceramic glazed tile, titanium fritted glaze is used as surface glaze, and titanium sphene is precipitated from a glaze layer to be used as a main crystal phase based on the titanium opalescence principle, so that the ceramic tile has a high reflection effect on sunlight, but the firing temperature range of the glaze of the ceramic glazed tile is narrow, the stability is poor at high firing temperature, and the glaze surface is Huang Fagong due to the slight change of firing atmosphere, so that the industrial production requirements of the reflective heat-insulation ceramic tile for building periphery and roof are difficult to meet.

Aiming at ceramic tiles used for building periphery and roofs, the water absorption rate is lower than 0.5%, the firing temperature is 1150-1250 ℃, and the stability of the titanium glaze as surface glaze at the temperature is insufficient. At present, the titanium glaze is stably applied to the following two aspects, namely, the titanium glaze is used as an impervious ground glaze layer (a make-up soil layer) of an inner wall brick with the firing temperature of below 1100 ℃, and the porosity of the glaze layer is high; and the second is used as enamel overglaze below 900 ℃, and the firing temperatures of the two are lower. The inventor previously raises the firing temperature of the titanium glaze, and conducts a plurality of experiments when the titanium glaze is debugged into a ceramic tile overglaze layer with high sunlight reflectance and good glaze performance, and as a result, the titanium overglaze is found to have a narrow firing range, and when the firing temperature is high, miliaria and overburning phenomena often occur, and tiny change of firing atmosphere can change the valence of titanium ions, so that the glaze surface develops Huang Fagong.

Therefore, in the present embodiment, a certain amount of TiO is contained in the reflective heat insulating glaze ₂ And ZrO ₂ And TiO introduced by titanium frit in the reflective heat-insulating glaze ₂ The mass percent of the zirconia is more than or equal to 4 percent, and ZrO is introduced by the zirconium white clinker ₂ The mass percentage of the glaze is more than or equal to 0.5 percent, so that the glaze can separate out high-content high-refractive-index crystalline phases such as titanium sphene, zirconium silicate, zirconium oxide and the like under the condition of quick firing of a roller kiln, and the glaze layer has high sunlight reflection ratio to the full wave band of sunlight.

In addition, active alumina powder (gamma-Al) is added into the raw materials for preparing the reflective heat-insulating glaze ₂ O ₃ ) The preparation method comprises the steps of mixing zirconia powder, titanium dioxide powder and quartz powder, adjusting the particle sizes of the zirconia powder, the titanium dioxide powder and the quartz powder, matching the components, improving the firing temperature of the reflective heat-insulation glaze, taking the prepared titanium-zirconium composite system glaze with low melting degree as a ground glaze layer at a high firing temperature, combining the ground glaze layer with a transparent cover glaze layer, enabling the ceramic tile to have high sunlight reflectance ratio, enabling the glaze layer not to generate Huang Fagong, and being good in stability at the high firing temperature.

Referring to fig. 1, the reflective insulation ceramic tile 100 includes a ceramic body layer 110, a ground glaze layer 120, a cover glaze layer 130 and a pattern layer 140, which are sequentially stacked, wherein the raw material for preparing the ground glaze layer 120 includes the reflective insulation glaze.

In one embodiment, the ceramic green body layer 110 has a water absorption of 0.5% or less. As the reflective heat-insulation ceramic tile 100 is applied outdoors, the water absorption is less than or equal to 0.5 percent.

In some embodiments, the firing temperature of ceramic green layer 110 is in the range of 1150 ℃ to 1250 ℃. As the reflective heat-insulation ceramic tile 100 is applied outdoors, the firing temperature of the ceramic green body layer 110 is 1150-1250 ℃.

In some embodiments, ceramic green body layer 110 may be a ceramic green body layer 110 used in conventional reflective insulation ceramic tile 100. In one embodiment, the chemical composition of ceramic green layer 110 includes, in mass percent: 60% -70% SiO ₂ 、17%~20% Al ₂ O ₃ 、5%~7% K ₂ O+Na ₂ O、2%~4% CaO+MgO、0.6%~2% Fe ₂ O ₃ +TiO ₂ And 4 to 7 percent of loss on ignition.

In other embodiments, ceramic green body layer 110 may be a lightweight insulating ceramic green body. The ceramic body layer 110 can generate heat insulation function for solar radiant heat transmitted and absorbed by the glaze layer of the reflective heat-insulation ceramic tile 100, thereby improving the performance of the reflective heat-insulation ceramic tile 100.

It is understood that in other embodiments, ceramic green body layer 110 may also be a poor whiteness green body. In the embodiment, the reflective heat-insulating glaze material is used as a raw material of the ground glaze layer, so that the firing temperature and the high-temperature viscosity of the traditional titanium system are improved, the glaze material has a higher initial melting point and a wider firing range, and can be adapted to ceramic body layers 110 with different qualities, thereby ensuring that the reflective heat-insulating ceramic tile 100 has a stable high sunlight reflectance function and a higher glaze quality.

In some embodiments, the thickness of the overglaze layer 120 is 0.2mm or more. The thickness of the ground coat layer 120 is small, and the reflection of sunlight is low. For the same glaze, the sunlight reflectance is increased to a certain extent as the thickness of the glaze layer is increased, but when the thickness of the ground glaze layer 120 exceeds a certain thickness, the glazing process is difficult, the production conditions of rapid drying and firing are not met, and the sunlight reflectance is not increased any more. Therefore, in the present embodiment, the thickness of the ground coat layer 120 is further 0.2mm to 1mm. For example, the thickness of the ground coat layer 120 may be, but is not limited to, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, or a range consisting of any two of these values.

In the present embodiment, the reflective insulating glaze is used as the glaze for the ground glaze layer 120, and is combined with the overglaze layer 130, and the overglaze layer 130 has the following characteristics: firstly, the transparency should be high so that the sunlight can be reflected out in a high proportion finally; then, titanium element is prevented from entering into the glass phase of the middle layer of the two layers in an ion form during high-temperature sintering to enable the glaze surface to be yellow; finally, the glaze surface should have the advantages of fineness, smoothness, pollution resistance, chemical corrosion resistance, good color development capability on ink-jet printing ink and the like. Therefore, in the present embodiment, the overglaze layer 130 is prepared by using a high-silicon, high-calcium, low-aluminum matte formula to reduce the ion migration between the overglaze layer 130 and the under glaze layer 120 at high temperature.

In one embodiment, the chemical composition of glaze layer 130 comprises, in mass percent: 50% -60% SiO ₂ 、5%~10% Al ₂ O ₃ 、0~2% B ₂ O ₃ 、1%~3% Na ₂ O、0~1% K ₂ O、15%~25% CaO、0~2% MgO、0~1% SrO、0~1% BaO、2%~4% ZnO、0~0.3% P ₂ O ₅ 、0~0.2% TiO ₂ 、0~0.3% Fe ₂ O ₃ And 5% -10% loss on ignition.

In some embodiments, the overglaze layer 130 is prepared from the following raw materials in percentage by mass: 5% -15% of transparent frit, 20% -40% of albite, 15% -25% of quartz, 12% -24% of calcite, 15% -25% of wollastonite, 0~3% of zinc oxide, 0~2% of barium carbonate, 0~2% of strontium carbonate and 5% -10% of kaolin. Wherein, by mass percent, the chemical composition of the transparent frit comprises: 55% -65% of SiO ₂ 、0~1%Na ₂ O、3%~5% K ₂ O、4%~7% Al ₂ O ₃ 、2%~6% B ₂ O ₃ 、0~2% MgO、10%~18% CaO、6%~10% ZnO、0~3% BaO、0~0.2% P ₂ O ₅ 、0~0.2% TiO ₂ 、0~0.2% Fe ₂ O ₃ And the ignition loss is less than or equal to 0.5 percent.

In some embodiments, the thickness of the overglaze layer 130 is 0.05mm to 0.2mm. For example, the thickness of overglaze layer 130 may be, but is not limited to, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.18mm, 0.2mm, or a range of any two of these values. The thickness does not affect the sunlight reflection ratio of the ground glaze layer 120, and simultaneously, the glaze surface of the reflective heat-insulating ceramic tile 100 has the performances of fine hand feeling, good stain resistance, chemical corrosion resistance and the like. Further, the thickness of the overglaze layer 130 is 0.05mm to 0.15mm.

By adopting the glaze layer 130, the reflective heat-insulation ceramic tile 100 has higher sunlight reflectance and good stability at higher firing temperature, and meanwhile, the decorative texture effect of the reflective heat-insulation ceramic tile 100 is enriched, and the fine touch feeling, stain resistance, chemical corrosion resistance and the like of the glaze surface are improved.

The inventor also finds out in experiments that the titanium glaze is used as the overglaze layer in the traditional technology, the following problems still exist: the glaze quality similar to that of a makeup soil layer or a ground glaze layer with low melting degree can be obtained, but the glaze layer has less glass phase, so that the glaze layer has the problems of easy dirt absorption, rough hand feeling and the like; when the conventional pigment or glaze material is added into the titanium glaze and the ceramic ink with the conventional color is printed on the surface of the glaze material through ink jet, titanium ions in the sintered glaze melt and pigment coloring ions are subjected to chemical reaction, so that color development is poor or color change is caused, and the product cannot form various designs and colors or a rich decorative effect.

The method is characterized in that 2% of pigments with different colors (the pigment types are the same as pigments for preparing ink-jet printing ink, such as wrapping red, wrapping yellow, cobalt-chromium-iron black, cobalt-aluminum blue and zinc-aluminum-iron-chromium brown pigments) are respectively added to a titanium series matt glaze and a zirconium series matt glaze, and color development after firing is observed, so that more miliaria bubbles and pinholes are formed on the titanium glaze surface, meanwhile, the color development of the titanium glaze on most pigments is lighter than that of the zirconium glaze, while the color development of the titanium glaze on the black pigment is changed into reddish brown and the color development of the yellowish brown is also reddish.

In the embodiment, the reflective heat-insulating glaze material is used as a preparation raw material of the ground glaze layer and is combined with the transparent cover glaze layer, so that the prepared reflective heat-insulating ceramic tile has the performances of fine and smooth hand feeling, high stain resistance, high chemical corrosion resistance and the like, has good color development capability on ink-jet printing ink, enriches the decorative texture effect of the ceramic tile, and can be combined with the ink-jet printing technology of the modern ceramic production technology to develop more personalized texture effect products.

In one embodiment, the patterned layer 140 is formed by ink-jet printing a ceramic ink. The pattern layer 140 is arranged on the reflective insulation ceramic tile 100, so that the decorative texture effect of the reflective insulation ceramic tile 100 is enriched, and the reflective insulation ceramic tile can be applied to application scenes such as the periphery of a building and a roof. Further, the overglaze layer 130 has good coloring ability for ink jet printing ink, and can form the pattern layer 140 by ink jet printing. Further, the pattern layer 140 is made of a light gray ink-jet printing line texture, which can reduce the area of the color zone without affecting the reflective insulation performance of the reflective insulation ceramic tile 100.

In some embodiments, reflective insulating ceramic tile 100 has a lightness L ≧ 90 and a solar reflectance L ≧ 100-0.15.

The reflective insulation ceramic tile 100 has at least the following advantages:

(1) The sunlight reflectance of the reflective insulation ceramic tile 100 meets the standard regulation of GB/T25261-2018 reflective insulation coating for buildings in the reflective insulation coating industry, can be suitable for building energy conservation in areas warm in winter and hot in summer, and has weather resistance, pollution resistance, service life, easy cleaning performance and strength which cannot be compared with coating materials.

(2) The reflective heat insulation ceramic tile 100 uses the reflective heat insulation glaze material of the titanium zirconium composite system as the ground glaze layer 120, so that the firing temperature and the high-temperature viscosity of the traditional titanium system are improved, the glaze material has a higher initial melting point and a wider firing range, and the reflective heat insulation ceramic tile 100 is ensured to have a stable high sunlight reflection ratio function and a higher glaze surface quality.

(3) The cover glaze layer 130 is added to the reflective heat-insulation ceramic tile 100, the cover glaze layer 130 has high transparency so that sunlight can be reflected in a high proportion finally, titanium elements can be prevented from entering a glass phase between the two layers in an ion form during high-temperature firing so that the glaze is yellow, the heat stability is further improved, in addition, the cover glaze layer 130 has fine and smooth touch, pollution resistance, chemical corrosion resistance, good color development capability on ink-jet printing ink and the like, the decorative texture effect of the reflective heat-insulation ceramic tile 100 is enriched, more personalized texture effect products can be developed by combining with the ink-jet printing technology of the modern ceramic production technology, and meanwhile, the glaze has the performances of fine and smooth hand feeling, high pollution resistance, high chemical corrosion resistance and the like.

The invention further provides a preparation method of the reflective insulation ceramic tile of the embodiment, which is a preparation method of the reflective insulation ceramic tile of the embodiment, please refer to fig. 2, the method specifically includes the following steps S210-S250:

step 210: a ceramic green body layer is prepared.

Step S220: and applying a ground coat on the surface of the ceramic body layer to form a ground coat layer.

In some embodiments, the ground coat layer is prepared by using a glaze slip having a specific gravity of 1.75g/cm ³ ~1.85g/cm ³ The glazing amount is 500g/m ² ~2500g/m ² 。

Specifically, a glaze pouring mode is adopted to apply the ground coat on the surface of the ceramic body layer to form the ground coat layer.

In some embodiments, step S220 includes: mixing the raw materials for preparing the ground glaze layer with water to make the specific gravity of the glaze slip be 1.75g/cm ³ ~1.85g/cm ³ Then applying the glaze layer on the surface of the ceramic body layer in a glaze pouring mode, and drying to form a ground glaze layer, wherein the glaze pouring amount is 500g/m ² ~2500g/m ² 。

In some embodiments, the thickness of the overglaze layer is 0.2mm or more. The thickness of the ground glaze layer is thin, and the sunlight reflection is low. For the same glaze, the sunlight reflectance is increased to a certain extent along with the increase of the thickness of the glaze layer, but when the thickness of the ground glaze layer exceeds a certain thickness, the glazing process is difficult, the production conditions of rapid drying and firing are not met, and the sunlight reflectance is not increased any more. Therefore, in the present embodiment, the thickness of the ground coat layer is 0.2mm to 1mm. For example, the thickness of the primer layer may be, but is not limited to, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, or a range consisting of any two of these values.

Step S230: and applying a surface glaze on the surface of the ground glaze layer to form a surface glaze layer.

In some embodiments, the overglaze layer is prepared by using glaze slip with specific gravity of 1.3g/cm ³ ~1.4g/cm ³ The glazing amount is 150g/m ² ~600g/m ² 。

Specifically, a glaze spraying mode is adopted to apply a surface glaze on the surface of the ground glaze layer to form a surface glaze layer. After the glaze spraying is finished, a drying step is also included.

In some embodiments, step S220 includes: mixing the raw materials for preparing the surface glaze layer with water to make the specific gravity of glaze slip be 1.3g/cm ³ ~1.4g/cm ³ Then applying the glaze layer on the surface of the ground glaze layer in a glaze spraying mode, and drying to form a surface glaze layer, wherein the glaze spraying amount is 150g/m ² ~600g/m ² 。

The glaze spraying mode is adopted in the glaze applying mode of the overglaze layer, so that the overglaze layer is relatively thin. The thickness is controlled to be 0.05-0.2mm, the sunlight reflection ratio of the ground glaze layer is not influenced by the thickness, and meanwhile, the glaze surface has the performances of fine hand feeling, good stain resistance, chemical corrosion resistance and the like.

Step S240: and performing ink-jet printing on the surface of the overglaze layer to form a pattern layer.

Step S250: after the pattern layer is prepared, firing at the firing temperature of 1150-1250 ℃ for 30-80 minutes to obtain a primary finished product of the ceramic tile; and edging the primary finished product of the ceramic tile to obtain the reflective heat-insulating ceramic tile.

In a specific example, the firing temperature may be, but is not limited to, 1150 ℃, 1180 ℃, 1200 ℃, 1220 ℃, 1250 ℃, or a range comprised of any two of these values. In one particular example, firing is performed in a roller kiln.

In some embodiments, the edging process may be a means commonly used in the art, such as polished tile, antique tile production processes.

In some embodiments, the reflective insulating ceramic tile has a water absorption of 0.5% or less.

The lightness L of the reflective heat-insulation ceramic tile with the light gray patterns prepared by the preparation method is more than or equal to 90, the sunlight reflection ratio is more than or equal to L/100-0.15, and the lightness L is higher than the standard requirement of GB/T25261-2018 reflective heat-insulation paint.

The preparation method of the reflective heat-insulation ceramic tile at least has the following advantages:

(1) The preparation method of the reflective heat-insulation ceramic tile is simple in process, and the titanium-zirconium composite opacification system is adopted to prepare the ground glaze layer, so that the firing temperature and the high-temperature viscosity of the system are improved, the firing range is widened, the stability of the solar reflective heat-insulation performance is improved, and the industrial production is easy to realize.

(2) The reflective heat-insulation ceramic tile has the advantages that the bottom glaze layer is matched with the surface glaze layer, the decorative effect of the ceramic tile is improved, more personalized products can be developed by combining with an ink-jet printing technology of a modern ceramic production technology, and meanwhile, the ceramic tile has the performances of fine and smooth hand feeling, high stain resistance, high chemical corrosion resistance and the like.

The invention also provides application of the reflective heat-insulation ceramic tile in building decoration or building energy conservation.

For the purposes and advantages of the present invention, the following detailed description of the reflective insulation ceramic tiles and the effects thereof is provided in connection with specific embodiments, it being understood that the specific embodiments described herein are only illustrative and should not be taken as limiting the invention. The following examples, unless otherwise specified, do not include other components except for inevitable impurities. The examples, which are not specifically illustrated, employ drugs and equipment, all of which are conventional in the art. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those in the literature, in books, or as recommended by the manufacturer.

Example 1

The embodiment provides a reflective heat-insulation ceramic tile which consists of a ceramic body layer, a ground glaze layer, a surface glaze layer and a pattern layer. The ceramic body layer comprises the following chemical compositions in percentage by mass: 65% SiO ₂ 、19.7% Al ₂ O ₃ 、2.8% K ₂ O、3.5% Na ₂ O、1.2% CaO、1.6% MgO、1.3% Fe ₂ O ₃ 、0.1% TiO ₂ And 4.8% loss on ignition; the ground coat layer comprises the following chemical components in percentage by mass: 54.12% SiO ₂ 、7.64% Al ₂ O ₃ 、0.35% B ₂ O ₃ 、0.68% Na ₂ O、1.20% K ₂ O、16.03% CaO、1.24% MgO、0.70% SrO、0.37% ZnO、10.42% TiO ₂ 、3.80% ZrO ₂ 、0.09% P ₂ O ₅ 、0.16% Fe ₂ O ₃ And 3.2% loss on ignition, thickness 0.28mm; the overglaze layer comprises the following chemical components in percentage by mass: 57.39% SiO ₂ 、7.85% Al ₂ O ₃ 、0.39% B ₂ O ₃ 、2.47% Na ₂ O、0.74% K ₂ O、19.04% CaO、0.32% MgO、0.01% SrO、0.26% BaO、2.66% ZnO、0.08% TiO ₂ 、0.02% P ₂ O ₅ 、0.18% Fe ₂ O ₃ And 8.59% loss on ignition, thickness 0.06mm.

The concrete preparation process of the reflective heat-insulation ceramic tile of the embodiment is as follows:

(1) Preparation of ceramic green body layer

The ceramic green body layer is prepared by mixing the raw materials according to the formula of the ceramic brick blank with the firing temperature of about 1200 ℃, and performing ball milling, spray granulation, compression molding and drying.

(2) Preparation of the ground glaze layer

Weighing the following preparation raw materials in percentage by mass: 45% of titanium frit, 10% of zirconium white frit, 18% of quartz powder and 3% of gamma-Al ₂ O ₃ 6% of titanium dioxide, 3% of zirconia powder, 5% of calcite, 4% of wollastonite, 1% of strontium carbonate and 5% of kaolin. The titanium frit comprises the following chemical components in percentage by mass: 58.70% SiO ₂ 、5.50% Al ₂ O ₃ 、1.21% Na ₂ O、2.32% K ₂ O、19.60% CaO、2.20% MgO、0.10% P ₂ O ₅ 、10.10% TiO ₂ 、0.12% Fe ₂ O ₃ And 0.15% loss on ignition. The chemical composition of the zirconium white frit is as follows by mass percent: 53.22% SiO ₂ 、2.92% Al ₂ O ₃ 、3.5% B ₂ O ₃ 、8% ZrO ₂ 、2.02% MgO、25.3% CaO、0.84% Na ₂ O、0.65% K ₂ O、3.26% ZnO、0.12% Fe ₂ O ₃ 、0.06% TiO ₂ And 0.11% loss on ignition. Zirconia powder, titanium dioxide powder and stone for measurement by laser particle sizerMedian particle diameter D of raw quartz powder ₅₀ 0.56 microns, 0.79 microns and 3.32 microns, respectively.

Mixing the above raw materials with water to make glaze slurry specific gravity 1.80g/cm ³ Then the mixture is sprayed on the green body, and the glazing amount is 720g/m ² And drying to obtain a ground coat layer with the thickness of 0.28 mm.

(3) Preparation of overglaze layer

Weighing the following preparation raw materials in percentage by mass: 12% transparent frit, 26.5% albite, 20% quartz, 16% calcite, 17% wollastonite, 1.5% zinc oxide and 7% kaolin. The transparent frit comprises the following chemical components in percentage by mass: 61.10% SiO ₂ 、5.98% Al ₂ O ₃ 、3.24% B ₂ O ₃ 、0.21% Na ₂ O、3.58% K ₂ O、13.58% CaO、0.16% MgO、2.13% BaO、9.69% ZnO、0.02% TiO ₂ 、0.05% P ₂ O ₅ 、0.1% Fe ₂ O ₃ And 0.16% loss on ignition.

Mixing the above raw materials with water to make glaze slurry specific gravity 1.35g/cm ³ Then spraying the glaze on the ground coat in a glaze spraying way, wherein the glazing amount is 200g/m ² And drying to obtain a surface glaze layer with the thickness of 0.06mm.

(4) Preparation of patterned layer

The patterns are printed with ceramic ink by ink jet to form a light gray level fine texture effect, so that the absorption of the color to sunlight can be reduced, the decorative effect of the reflective heat-insulation ceramic tile is improved, and meanwhile, the reflective heat-insulation ceramic tile has reflective heat-insulation performance.

(5) Firing into

And (3) feeding the obtained ceramic tile semi-finished product into a roller kiln to be sintered at the sintering temperature of 1195 ℃ for 47min, and then performing edge grinding treatment to obtain the reflective heat-insulation ceramic tile of the embodiment.

The Lab color difference meter detects that the L/a/b of the reflective heat-insulation ceramic tile is 96.28/-0.91/2.31, and simultaneously detects the sunlight full-wave-band reflectance ratio of the reflective heat-insulation ceramic tile according to the standard ASTM E1980-11, and the detection result is 0.9, the emissivity is 0.8, and the Solar Reflection Index (SRI): low wind speed environmenth _c =5Wm ^-2 K ^-1 Next, the SRI was 112.6; wind velocity environmenth _c =12Wm ^-2 K ^-1 Next, the SRI was 112.9; high wind speed environmenth _c =30Wm ^-2 K ^-1 Next, the SRI was 113.2. Meanwhile, other properties of the ceramic tile can meet the requirements of the national standard GB/T4100.

As shown in fig. 3, XRD analysis results of the ground coat layer of the reflective heat-insulating ceramic tile according to the present example revealed that titanium sphene, zirconium silicate and zirconium oxide crystals having high refractive indices were precipitated in the ground coat layer.

The XRD analysis result of the overglaze layer is shown in figure 4, and it can be seen from the figure that the overglaze layer precipitates calcium silicate crystals with low refractive index, so that the glaze layer is transparent, the function of high sunlight reflectance of the underglaze layer is not influenced, and meanwhile, the glaze surface has good sub-light effect, and the glossiness is 30 degrees through testing.

Example 2

The structure and the preparation steps of the reflective heat-insulation ceramic tile are similar to those of the ceramic tile in the embodiment 1, the difference is that the preparation raw materials and the chemical compositions of the ground coat layer are different, the using amounts of zirconium oxide powder and zirconium silicate are increased on the basis of the ceramic tile in the embodiment 1, the content of zirconium dioxide in the ground coat layer is increased, and the rest is the same as that in the ceramic tile in the embodiment 1. Specifically, the preparation raw materials of the ground coat layer of this example are as follows by mass percent: 40.9% titanium frit, 9.09% zirconium white frit, 16.36% quartz powder, 2.73% gamma-Al ₂ O ₃ 5.45 percent of titanium dioxide, 7.27 percent of zirconia powder, 4.55 percent of zirconium silicate, 4.55 percent of calcite, 3.64 percent of wollastonite, 0.91 percent of strontium carbonate and 4.55 percent of kaolin powder. The ground coat layer comprises the following chemical components in percentage by mass: 50.70% SiO ₂ 、6.98% Al ₂ O ₃ 、0.32% B ₂ O ₃ 、0.62% Na ₂ O、1.09% K ₂ O、14.58% CaO、1.13% MgO、0.64% SrO、0.34% ZnO、9.48% TiO ₂ 、10.96% ZrO ₂ 、0.10% P ₂ O ₅ 、0.15% Fe ₂ O ₃ And 2.91% loss on ignition.

The experimental result shows that although the reflective heat-insulation ceramic tile of the embodiment detects that L is 95.83, the sunlight reflection ratio is 0.88 and is greater than L/100-0.15, the reflective heat-insulation ceramic tile meets the requirements, and the glaze layer does not turn yellow and turn red, the excessive zirconium dioxide raw material not only increases the formula cost, but also does not improve the sunlight reflection ratio any more, in addition, the excessive zirconium dioxide influences the firing temperature of the glaze and the expansion coefficient of the glaze layer, so that the ground glaze layer is not completely sintered, when the ground glaze layer is applied, the glaze orange peel phenomenon easily occurs in the reflective heat-insulation ceramic tile, and the ceramic tile is deformed and cracked in the later period when the roof is exposed to the sun and rainwater because the ground glaze is not sintered.

Example 3

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, except that the preparation raw materials and the chemical composition of the ground coat layer are different, and the rest is the same as that of the embodiment 1. Specifically, the preparation raw materials of the ground coat layer of this example are as follows by mass percent: 40% of titanium frit, 19% of zirconium white frit, 14% of quartz powder and 1% of gamma-Al ₂ O ₃ 7% of titanium dioxide, 5% of zirconia powder, 8% of calcite, 1% of wollastonite and 5% of kaolin. The chemical composition of the under-glaze layer of this example is as follows in mass percent: 50.42% SiO ₂ 、5.63% Al ₂ O ₃ 、0.67% B ₂ O ₃ 、0.68% Na ₂ O、1.13% K ₂ O、17.57% CaO、1.3% MgO、0.66% ZnO、10.95% TiO ₂ 、6.52% ZrO ₂ 、0.09% P ₂ O ₅ 、0.15% Fe ₂ O ₃ And 4.23% loss on ignition.

Example 4

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, except that the preparation raw materials and the chemical composition of the ground coat layer are different, and the rest is the same as that of the embodiment 1. Specifically, the preparation raw materials of the ground glaze layer of the embodiment are as follows by mass percent: 40% titanium frit, 10% zirconium white frit, 18.3% quartz powder, 3% gamma-Al ₂ O ₃ 4% of titanium dioxide, 1.2% of zirconia powder, 10.5% of calcite, 7% of wollastonite, 1% of barium carbonate and 5% of kaolin. The particle size of the zirconia powder was 0.4. Mu.m. The chemical composition of the under-glaze layer of this example is as follows in mass percent: 52.9% SiO ₂ 、7.37% Al ₂ O ₃ 、0.35% B ₂ O ₃ 、0.62% Na ₂ O、1.09% K ₂ O、19.50% CaO、1.16% MgO、0.37% ZnO、0.78% BaO、8% TiO ₂ 、2% ZrO ₂ 、0.08% P ₂ O ₅ 、0.16% Fe ₂ O ₃ And 5.62% loss on ignition.

Example 5

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, except that the preparation raw materials and the chemical composition of the ground coat layer are different, and the rest is the same as that of the embodiment 1. Specifically, the preparation raw materials of the ground coat layer of this example are as follows by mass percent: 51% titanium frit, 15% zirconium white frit, 10% quartz powder, 1% gamma-Al ₂ O ₃ 10% of titanium dioxide, 5% of zirconia powder, 3% of zirconium silicate and 5% of kaolin. The particle size of the zirconia powder was 0.7. Mu.m. The chemical composition of the under-glaze layer of this example is as follows in mass percent: 51.3% SiO ₂ 、6.13% Al ₂ O ₃ 、0.53% B ₂ O ₃ 、0.78% Na ₂ O、1.36% K ₂ O、13.82% CaO、1.44% MgO、0.52% ZnO、15% TiO ₂ 、8.1% ZrO ₂ 、0.14% P ₂ O ₅ 、0.17% Fe ₂ O ₃ And 0.71% loss on ignition.

Example 6

The structure and the preparation steps of the reflective heat-insulation ceramic tile are similar to those of the ceramic tile in the embodiment 1, and the difference is that the particle sizes of titanium dioxide and quartz powder selected from the raw materials of the ground glaze layer are different, the median particle sizes of the titanium dioxide and the quartz powder in the embodiment are both larger than those in the embodiment 1, and D is larger than that in the embodiment 1 ₅₀ 4.8 microns and 12.7 microns respectively, otherwise the same as in example 1.

Example 7

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, except that the glaze applying amount is different in the process of preparing the ground glaze layer, and the glaze applying amount is 1060g/m which is higher than that of the embodiment 1 ² The final primer layer was 0.42mm thick, and the rest was the same as in example 1.

Example 8

The structure and preparation steps of the reflective heat-insulation ceramic tile are similar to those of the ceramic tile in the embodiment 1, and the difference is that the glazing amount is not required in the process of preparing the overglaze layerMeanwhile, the glazing amount is 460g/m which is higher than that of the embodiment 1 ² The thickness of the overglaze layer was 0.14mm, and the procedure was otherwise the same as in example 1.

Example 9

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, and the difference is that the glazing amount is increased to 850g/m in the process of preparing the overglaze layer and is different ² The thickness of the overglaze layer was about 0.26mm, and the rest was the same as in example 1.

Experiments prove that when the surface glaze layer is thicker, the sunlight reflection ratio of the reflective heat-insulation ceramic tile is 0.86, and compared with the example 1, the sunlight reflection ratio of the reflective heat-insulation ceramic tile is slightly reduced.

Example 10

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, except that the glazing amount is reduced to 70g/m in the process of preparing the overglaze layer and is different ² The thickness of the overglaze layer is about 0.02mm. The rest is the same as in example 1.

Experiments prove that the reflection ratio of the reflective heat-insulation ceramic tile in the embodiment is 0.88, the reflection ratio is slightly reduced compared with that in embodiment 1, the glaze surface does not turn yellow or turn red, but the glaze coating amount of the overglaze layer is too low, and the glaze spraying process is difficult to realize uniform glaze coating, so that the glaze surface is rough and uneven.

Example 11

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the embodiment are similar to those of the embodiment 1, and the difference is that the ceramic green body layer is different, the raw material used by the ceramic green body layer is poor, and the raw material is mainly Fe in chemical composition ₂ O ₃ 、TiO ₂ And the loss on ignition is higher. The chemical composition of the ceramic green body layer of this example is as follows in mass percent: 64.4% SiO ₂ 、18.4% Al ₂ O ₃ 、2.7% K ₂ O、3.3% Na ₂ O、1.1% CaO、1.4% MgO、1.8% Fe ₂ O ₃ 、0.3% TiO ₂ And 6.6% loss on ignition. The rest is the same as in example 1.

Comparative example 1

The construction and preparation procedure of the reflective insulation ceramic tile of this comparative example are similar to those of example 1, except that the bottomThe glaze layer was prepared from the same raw materials and chemical compositions as in example 1, except that the raw materials contained no zirconium white frit and no zirconium oxide powder. The preparation raw materials of the ground coat layer of the comparative example are as follows by mass percent: 55% of titanium frit, 18% of quartz powder and 4% of gamma-Al ₂ O ₃ 8% of titanium dioxide, 5% of calcite, 4% of wollastonite, 1% of strontium carbonate and 5% of kaolin powder. The ground coat layer comprises the following chemical components in percentage by mass: 54.61% SiO ₂ 、8.89% Al ₂ O ₃ 、0.72% Na ₂ O、1.37% K ₂ O、15.46% CaO、1.26% MgO、0.70% SrO、0.06% ZnO、13.44% TiO ₂ 、0.12% P ₂ O ₅ 、0.16% Fe ₂ O ₃ And 3.21% loss on ignition.

Comparative example 2

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the example 1, except that the preparation raw material proportion of the ground coat layer is different, the use amount of the titanium frit and the zirconium white frit is reduced, and the rest is the same as that of the example 1. Specifically, the preparation raw materials of the ground coat layer of the comparative example are as follows by mass percent: 29.22 percent of titanium frit, 4.87 percent of zirconium white frit, 21.72 percent of quartz powder, 1.06 percent of albite, 4.63 percent of potassium feldspar and 3.25 percent of gamma-Al ₂ O ₃ 7.69 percent of titanium dioxide, 3.44 percent of zirconia powder, 4.87 percent of calcite, 13.46 percent of wollastonite, 1.04 percent of strontium carbonate and 4.75 percent of kaolin.

The ground coat layer comprises the following chemical components in percentage by mass: 54.09% SiO ₂ 、7.62% Al ₂ O ₃ 、0.17% B ₂ O ₃ 、0.68% Na ₂ O、1.15% K ₂ O、16.11% CaO、1.21% MgO、0.73% SrO、0.36% ZnO、10.51% TiO ₂ 、3.83% ZrO ₂ 、0.09% P ₂ O ₅ 、0.16% Fe ₂ O ₃ And 3.29% loss on ignition.

Although the preparation raw material for the under coat layer of this comparative example was the same as that of example 1 and the chemical composition was not much different from that of example 1, tiO introduced in the form of titanium frit was used ₂ Content less than 4%, zrO introduced by zirconium white frit ₂ Less than 0.5%. Under the condition of quick firing in a roller kiln, the bottom glaze layer does not reach the sintering degree,the amount of generated titanium sphene is low, and the generated titanium sphene is introduced into TiO in the form of titanium dioxide ₂ The components can not be completely generated into titanium sphene, and rutile or titanium ions enter a glass phase to cause the glaze surface to be yellowish, and finally, the reflectivity of the titanium sphene to the infrared band of sunlight is low, so that the sunlight reflectivity is lower than the standard of a reflective coating.

Comparative example 3

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the ceramic tile in example 1, except that the grain sizes of the zirconia powder selected in the raw materials for preparing the ground coat layer are different, the median grain size of the zirconia powder of the comparative example is larger than that of the ceramic tile in example 1, and D is larger than that of the ceramic tile in example 1 ₅₀ Is 0.8 μm, otherwise the same as in example 1.

The reflective heat insulation ceramic tile of the comparative example is characterized in that the reflection of the zirconia crystal phase with large particle size to the sunlight visible light wave band is low. The reflective heat-insulating ceramic tile of the comparative example has an L value lower than 90, and the glaze surface is yellowish, and the solar reflectance ratio does not meet the reflective coating standard.

Comparative example 4

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the ceramic tile in example 1, except that the grain sizes of the zirconia powder selected in the raw materials for preparing the ground coat layer are different, the median grain size of the zirconia powder of the comparative example is larger than that of the ceramic tile in example 1, and D is larger than that of the ceramic tile in example 1 ₅₀ Is 0.3 μm, the rest being the same as in example 1.

Comparative example 5

The construction and manufacturing procedure of the reflective heat-insulating ceramic tile of this comparative example were similar to those of example 1, except that alpha-Al was used as the material for the ground coat layer ₂ O ₃ Alternative Gamma-Al in example 1 ₂ O ₃ The mass percentage was still 3%, and the rest was the same as in example 1.

The experimental results show that the alumina (alpha-Al) is calcined ₂ O ₃ ) The mode introduces the reflective heat-insulation ceramic ground glaze which mainly comprises titanium frit and matte zirconium white frit, the melting temperature of the reflective heat-insulation ceramic ground glaze cannot be increased, so that miliaria bubbles appear on the ground glaze surface at a high firing temperature (when a color glaze layer is applied, pinholes appear on the glaze surface), and the glaze surface turns yellow.

Comparative example 6

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the example 1, and the difference is that the preparation raw material proportion of the ground coat layer is different, titanium dioxide is not contained, and the rest is the same as that of the example 1. Specifically, the comparative example is prepared from the following raw materials in percentage by mass: 80% of titanium frit, 8% of zirconium frit, 2% of quartz powder and 2% of gamma-Al ₂ O ₃ 2% of zirconia powder, 1% of calcite and 5% of kaolin. The ground coat layer comprises the following chemical components in percentage by mass: 55.61% SiO ₂ 、8.44% Al ₂ O ₃ 、0.28%B ₂ O ₃ 、0.97% Na ₂ O、1.98% K ₂ O、18.26% CaO、1.93% MgO、0.34%ZnO、8.10% TiO ₂ 、2.64% ZrO ₂ 、0.10% P ₂ O ₅ 、0.19 Fe ₂ O ₃ And 1.16% loss on ignition.

Comparative example 7

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the example 1, except that the preparation raw materials and the chemical composition ratio of the ground glaze layer are different, and the rest is the same as that of the example 1. Specifically, the preparation raw materials of the ground coat layer of the comparative example are as follows by mass percent: 50% of titanium frit, 10% of zirconium white frit, 14% of quartz powder and 2% of gamma-Al ₂ O ₃ 11.12 percent of titanium dioxide, 2.88 percent of zirconia powder, 4 percent of wollastonite, 1 percent of strontium carbonate and 5 percent of kaolin. The chemical composition of the under-glaze layer of this example is as follows in mass percent: 53.07% SiO ₂ 、6.83% Al ₂ O ₃ 、0.35% B ₂ O ₃ 、0.74% Na ₂ O、1.31% K ₂ O、14.25% CaO、1.34% MgO、0.38% ZnO、0.70% SrO、16% TiO ₂ 、3.68% ZrO ₂ 、0.13% P ₂ O ₅ 、0.16% Fe ₂ O ₃ And 1.06% loss on ignition.

Comparative example 8

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the example 1, and the difference is that the glazing amount is different in the process of preparing the ground glaze layer, and the glazing amount is less than that of the example 1 and is 280g/m ² The final ground coat layer was 0.11mm thick. The rest is the same as in example 1.

Comparative example 9

The construction and preparation procedure of the reflective insulation ceramic tile of this comparative example were similar to those of example 1, except that the ceramic tile of this comparative example did not contain a glaze layer. The rest is the same as in example 1.

Comparative example 10

The structure and the preparation steps of the reflective heat-insulation ceramic tile of the comparative example are similar to those of the example 1, and the difference is that the overglaze layer is different, the overglaze layer adopts transparent protective glaze of the archaized tile, and the reflective heat-insulation ceramic tile comprises the following chemical components in percentage by mass: 52.01% SiO ₂ 、16.23% Al ₂ O ₃ 、0.39% B ₂ O ₃ 、2.60% Na ₂ O、0.77% K ₂ O、12.92% CaO、2.39% MgO、0.01% SrO、4.60% BaO、3.74% ZnO、0.08% TiO ₂ 、0.20% P ₂ O ₅ 、0.37% Fe ₂ O ₃ And 3.69% loss on ignition. The rest is the same as in example 1.

Performance testing

The reflective and heat-insulating ceramic tile samples prepared in the embodiments 1 to 11 and the comparative examples 1 to 10 are tested for reflective and heat-insulating properties, and the stability of the glaze quality is judged, wherein the stability of the glaze quality comprises whether the glaze is Huang Fagong, the glaze matte effect (the glossiness is preferably 10 to 40, if the glossiness is too high, light pollution is generated, the design requirement of diffuse reflection of the reflective and heat-insulating ceramic tile is not facilitated), the color of the glaze is changed, whether the glaze has pinhole miliaria bubbles and other defects. In addition, the other performances specified by the national standards of the ceramic tiles, such as pollution resistance, chemical corrosion resistance, thermal shock resistance, glaze defects, deformation degree, color difference and the like, of the glazed tiles are mainly detected from the use scene of the products. The detection of the reflective heat-insulating property refers to the standard specification of ASTM C1483/C1483M building external solar radiation prevention coating to measure the solar light reflectance, and the GB/T25261-2018 standard of the reflective heat-insulating coating industry is specified, when the lightness L of the material is more than or equal to 90, the solar light reflectance is more than or equal to L/100-0.15, the material meeting the solar light reflectance has good reflective heat-insulating function; glaze stability is mainly determined by visual inspection; the other properties of the reflective heat-insulation ceramic tile are detected by the method described in the national standard GB/T3810. The results are shown in tables 1 and 2 below:

TABLE 1 Performance test results for reflective insulation ceramic tiles

TABLE 2 Performance test results for reflective insulation ceramic tiles

It can be seen from the above table that the composition and proportion of the ground glaze layer are adjusted to match the ground glaze layer with the surface glaze layer, so that the lightness L of the reflective heat-insulating ceramic tile is more than or equal to 90, the sunlight reflection ratio is more than or equal to L/100-0.15, and the glaze surface has good quality and no yellowing and redness when being fired at high temperature.

The addition of a certain amount of zirconium dioxide into the ground coat layer can improve the sunlight reflectance and the firing temperature, but when the amount of zirconium dioxide is more than the amount of zirconium dioxide, the sunlight reflectance is not improved any more, but the ground coat layer is not completely sintered, the water absorption rate of the reflective heat-insulating ceramic tile is higher, and the possibility of later deformation exists. In addition, the glaze quality can be further improved by adjusting the thickness, the composition and the like of the ground glaze layer and the glaze layer, so that the glossiness meets the diffuse reflection design requirement of the reflective heat-insulation ceramic tile.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.

Claims (10)

1. The reflective heat-insulating glaze is characterized by comprising the following raw materials in parts by weight: titanium frit, zirconium white frit, zirconia powder, titanium dioxide and activated alumina powder;

the reflective heat-insulating glaze contains TiO ₂ The mass percent of the reflective heat-insulation glaze is 8-15%, and the mass percent of TiO in the reflective heat-insulation glaze is more than or equal to 4% ₂ From the titanium frit;

the reflective heat-insulating glaze contains ZrO ₂ The mass percent of the ZrO is more than or equal to 2 percent, and the mass percent of the ZrO in the reflective heat-insulating glaze is more than or equal to 0.5 percent ₂ From the zirconium white frit;

in the preparation raw materials, the median particle size of the zirconia powder is 0.4-0.7 μm.

2. The reflective insulating glaze according to claim 1, wherein the reflective insulating glaze comprises the following chemical components in percentage by mass: 50% -60% SiO ₂ 、5%~12% Al ₂ O ₃ 、8%~15% TiO ₂ 、2%~8% ZrO ₂ 、0.5%~2% K ₂ O、0~1% Na ₂ O、0~1% B ₂ O ₃ 、12%~20% CaO、1%~2% MgO、0~2% BaO、0~2% SrO、0~1% ZnO、0~1% P ₂ O ₅ 、0~0.2% Fe ₂ O ₃ And 0~8% loss on ignition.

3. The reflective insulating glaze according to claim 1, wherein the reflective insulating glaze is prepared from the following raw materials in percentage by mass: 40-60% of titanium frit, 10-20% of zirconium white frit, 10-20% of quartz powder, 0< active alumina powder is less than or equal to 5%, 3-10% of titanium dioxide, 1-5% of zirconia powder, 0~5% of zirconium silicate, 0-15% of calcite, 0-10% of wollastonite, 0~3% of dolomite, 0~3% of barium carbonate, 0~3% of strontium carbonate, 5-10% of kaolin, 0~5% of potassium feldspar, 0~5% of sodium feldspar and 0~5% of calcined talc;

in the preparation raw materials, median particle diameters of the zirconia powder, the quartz powder and the titanium dioxide are respectively 0.4-0.7 μm, 2-4 μm and 0.6-1 μm.

4. The reflective insulating frit according to claim 3, wherein the chemical composition of the titanium frit comprises, in mass%: 50% -60% SiO ₂ 、8%~12% TiO ₂ 、4%~6% Al ₂ O ₃ 、0~3% MgO、18%~25% CaO、1%~2% Na ₂ O、1%~3% K ₂ O、0~0.3% Fe ₂ O ₃ 、0~1% P ₂ O ₅ And the ignition loss is less than or equal to 0.3 percent;

the zirconium white frit comprises the following chemical compositions in percentage by mass: 50% -60% SiO ₂ 、2%~5% Al ₂ O ₃ 、2%~5% B ₂ O ₃ 、7%~10% ZrO ₂ 、1%~3% MgO、22%~30% CaO、0.5%~1.5% Na ₂ O、0.5%~1% K ₂ O、2%~5% ZnO、0~0.3% Fe ₂ O ₃ 、0~0.2% TiO ₂ And the ignition loss is less than or equal to 0.3 percent.

5. A reflective insulation ceramic tile, comprising a ceramic body layer, a ground coat layer, a cover coat layer and a pattern layer which are sequentially stacked, wherein the ground coat layer is prepared from the reflective insulation glaze material of claim 1~4.

6. The reflective insulation ceramic tile as claimed in claim 5, wherein the thickness of the ground glaze layer is more than or equal to 0.2mm; the thickness of the overglaze layer is 0.05mm to 0.2mm.

7. The reflective insulating ceramic tile of claim 5, wherein the overglaze layer satisfies at least one of the following conditions:

(1) The chemical composition of the overglaze layer comprises the following components in percentage by mass: 50% -60% SiO ₂ 、5%~10% Al ₂ O ₃ 、0~2% B ₂ O ₃ 、1%~3% Na ₂ O、0~1% K ₂ O、15%~25% CaO、0~2% MgO、0~1% SrO、0~1% BaO、2%~4% ZnO、0~0.3% P ₂ O ₅ 、0~0.2% TiO ₂ 、0~0.3% Fe ₂ O ₃ And 5% -10% loss on ignition;

(2) The overglaze layer is prepared from the following raw materials in percentage by mass: 5% -15% of transparent frit, 20% -40% of albite, 15% -25% of quartz, 12% -24% of calcite, 15% -25% of wollastonite, 0~3% of zinc oxide, 0~2% of barium carbonate, 0~2% of strontium carbonate and 5% -10% of kaolin;

wherein the chemical composition of the transparent frit comprises, by mass: 55% -65% of SiO ₂ 、0~1%Na ₂ O、3%~5% K ₂ O、4%~7% Al ₂ O ₃ 、2%~6% B ₂ O ₃ 、0~2% MgO、10%~18% CaO、6%~10% ZnO、0~3% BaO、0~0.2% P ₂ O ₅ 、0~0.2% TiO ₂ 、0~0.2% Fe ₂ O ₃ And the ignition loss is less than or equal to 0.5 percent.

8. The reflective insulating ceramic tile of any one of claims 5~7, wherein said reflective insulating ceramic tile has a lightness L ≥ 90 and a solar reflectance L ≥ 100-0.15.

9. A method for making a reflective insulation ceramic tile, the reflective insulation ceramic tile defined in any one of claims 5~8, the method comprising the steps of:

(1) Preparing the ceramic green body layer;

(2) Applying a ground coat on the surface of the ceramic blank body layer to form the ground coat layer;

(3) Applying a surface glaze on the surface of the ground glaze layer to form the surface glaze layer;

(4) Ink-jet printing is carried out on the surface of the overglaze layer to form the pattern layer;

(5) After the pattern layer is prepared, firing at the firing temperature of 1150-1250 ℃ for 30-80 minutes to obtain a primary finished product of the ceramic tile; edging the primary finished product of the ceramic tile to obtain the reflective heat-insulating ceramic tile;

wherein, in the preparation of the ground glaze layer, the specific gravity of the glaze slip is 1.75g/cm ³ ~1.85g/cm ³ The glazing amount is 500g/m ² ~2500g/m ² ；

In the preparation of the surface glaze layer, the specific gravity of the glaze slip is 1.3g/cm ³ ~1.4g/cm ³ The glazing amount is 150g/m ² ~600g/m ² 。

10. Use of the reflective insulating ceramic tile of any one of claims 5~8 in architectural decoration or energy conservation for buildings.

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