Preparation method of blushing physically colored architectural ceramics

Abstract

The present invention belongs to the technical field of surface decoration of architectural ceramics, and specifically relates to a method for preparing architectural ceramics with a blushing physical coloration. The preparation method comprises the following steps: step (1) applying a base glaze to the surface of a ceramic tile blank and drying it; step (2) applying an effect glaze to the surface of the dried ceramic tile blank after the base glaze is applied and drying it; step (3) firing and edge-grinding the dried ceramic tile blank after the effect glaze is applied, thereby preparing the blushing physical coloration architectural ceramics. The present invention achieves the preparation of blushing architectural ceramics by utilizing the composite physical coloration of glass-crystallization by regulating the phase separation and crystallization properties of the architectural ceramic glaze layer.

Description

Technical Field

[0001] The invention belongs to the technical field of surface decoration of building ceramics, and particularly relates to a method for preparing blush-colored physically colored building ceramics. Background Art

[0002] With the continuous development of my country's national economy and the improvement of people's living standards, consumers' aesthetic appreciation and appreciation are also continuously improving, leading to a greater emphasis on deriving aesthetic enjoyment from architectural decorative environments. Consequently, people's decorative requirements for architectural ceramics are gradually increasing, with a greater emphasis on personalization and decorative effects. Currently, architectural ceramics are primarily colored and patterned using inkjet printing. This primarily utilizes chemical colors (pigment colors), which utilize the selective absorption of light by colorants / pigments in the ink to achieve color. Chemical colors offer high controllability and facilitate large-scale product replication; however, the coloring effect is monotonous and lacks flexibility.

[0003] Structural color rendering technology, also known as physical coloring, does not contain any coloring chemical elements. Instead, it primarily uses the material's microstructure to selectively reflect, scatter, interfere, or diffract light to create color. Compared to chemical color, structural color is solely dependent on the material's microstructure, resulting in significantly better color durability. Without the use of chemical pigments, the coloring method is more environmentally friendly. Furthermore, structural color is more sensitive to light and often exhibits angular chromatic aberration or iridescence. For example, Jun porcelain glazes, Tianmu glazes, and celadon glazes all contain a wealth of structural colors, creating a unique and wonderful visual experience of light and color, thereby enhancing the decorative effect of ceramic products.

[0004] Given the unique decorative effects of physical coloring, a series of research and development efforts are underway for physical coloring technologies for architectural ceramics. Patents CN106431504A, CN103288492B, and CN109180220A all utilize photonic crystal films deposited on the glaze layer of sintered architectural ceramics, leveraging the periodic arrangement of the photonic crystals to achieve physical coloring. However, these methods require relatively low heat treatment temperatures (500-900°C) for the photonic crystal films, resulting in poor mechanical properties and durability. Furthermore, the secondary sintering heat treatment increases manufacturing costs and reduces production efficiency. Patents CN117843395A and CN221777980U utilize femtosecond lasers to finely process architectural ceramic glazes or coatings, utilizing the resulting periodic arrangement of micro-nanostructures to achieve physical coloring. However, these methods require high equipment requirements, making industrial application difficult. In addition, patents with publication numbers CN105712630A and CN119350063A achieve physical coloring through ceramic glaze layer formulation and structural design, utilizing the spectral response characteristics of the precipitated crystalline phase. However, such methods use a large amount of rare earth metals and rare metal oxides / compounds (niobium oxide, cerium oxide, yttrium oxide, scandium oxide, vanadium oxide, ammonium molybdate, tungsten oxide, etc.), resulting in high raw material costs and difficulty in large-scale application.

[0005] "Blushing" refers to the phenomenon in which ceramic glazes appear to have a purple-red hue when exposed to light. This phenomenon is common in traditional Ru porcelain and is a key characteristic in its identification. This subtle blushing of the glaze surface, shifting with the light, appears and disappears, and creates a jade-like, beautiful effect that greatly enhances the decorative effect of ceramics. However, the formation mechanism of this blushing phenomenon in Ru porcelain is not fully understood, and the high-temperature reduction firing method used in traditional Ru porcelain is difficult to apply to the manufacture of architectural ceramics. Consequently, there is no research or development of purple-red iridescent architectural ceramic products, either domestically or internationally. Furthermore, the aforementioned physical coloring techniques are unable to achieve this decorative blushing effect in architectural ceramics. Summary of the Invention

[0006] In view of this, the present invention achieves the preparation of blush-colored architectural ceramics by regulating the phase separation and crystallization properties of the architectural ceramic glaze layer and utilizing the composite physical coloring of glass and crystallization. The present invention adopts the following technical solutions to achieve the above-mentioned purpose:

[0007] The present invention provides a method for preparing blush-colored physically colored architectural ceramics. The preparation method comprises the following steps:

[0008] Step (1) applying a base glaze on the surface of the ceramic tile and performing a drying process;

[0009] Step (2) applying effect glaze to the surface of the dried ceramic tile blank after applying the base glaze, and performing a drying process;

[0010] Step (3) The dried ceramic tile blanks after applying the effect glaze are fired and edge-grinded to obtain blush-colored physical colored architectural ceramics.

[0011] Preferably, the chemical composition of the base glaze includes, by mass percentage, SiO2 53-60%; Al2O3 25-30%; Fe2O3 0.2-0.5%; TiO2 0.1-0.2%; CaO 0.3-0.8%; MgO 0.1-0.5%; K2O 2-6%; Na2O 2-3.5%; ZrO2 4-8%; and loss on ignition 2-5%.

[0012] Preferably, the specific gravity of the base glaze is 1.40-1.45 g / cm 3 , glaze application amount is 500~650 g / m 2 The base glaze is applied by pouring or spraying.

[0013] Preferably, the chemical composition of the effect glaze includes, by mass percentage, SiO2 30-42%; Al2O3 5-9%; TiO2 10-20%; CaO 5-8%; MgO 0.5-1.2%; K2O 2.5-4%; Na2O 0.5-1%; BaO 0.5-1%; ZnO 20-34%; ZrO2 2.5-8%; and loss on ignition 0.4-1.1%.

[0014] Preferably, the mineral composition of the effect glaze includes, by mass, 40-60 parts of calcium-zinc low-temperature frit, 4-10 parts of kaolin, 16-30 parts of calcined zinc oxide, 10-20 parts of titanium dioxide, and 4-12 parts of zircon; wherein the chemical composition of the calcium-zinc low-temperature frit includes, by mass percentage, SiO2 45-60%; Al2O3 5-10%; CaO 10-15%; MgO 1-3%; K2O 5-8%; Na2O 1-2%; BaO 1-2%; and ZnO 5-10%.

[0015] Preferably, the specific gravity of the effect glaze is 1.60-1.80 g / cm 3 , glaze application amount is 600~900 g / m 2 The effect glaze is applied by pouring or spraying.

[0016] Preferably, the sintering temperature is 1130-1160° C., and the sintering time is 35-60 min.

[0017] Preferably, the fired effect glaze has a layered structure of crystallization-amorphous-crystallization, and crystallization occurs preferentially at the base glaze-effect glaze interface and on the surface of the effect glaze.

[0018] Preferably, the amorphous phase has a distinct phase separation structure, is in the form of isolated spherical droplets, and has a short-range order in distribution.

[0019] Preferably, the crystallization phase on the surface of the effect glaze after firing is mainly rutile crystal phase, and the rutile has an obvious preferred orientation, and the preferred orientation crystal plane is (110).

[0020] Preferably, the coupled superposition of Bragg scattering of amorphous phase droplets and rutile crystallization coloring promotes the formation of purple-red iridescence on the effect glaze surface.

[0021] The present invention has the following beneficial effects:

[0022] This invention, based on a design of architectural ceramic glaze formulations, utilizes the crystallization capacity of the effect glaze to produce a ceramic glaze with a crystallized-amorphous-crystallized layered structure. By leveraging the coupled Bragg scattering of the amorphous phase and the coloration of TiO2 (rutile) crystallization, a purple-red iridescence is created within the ceramic glaze, enhancing the decorative effect of architectural ceramic products. Furthermore, the surface of the glaze layer of the resulting physically colored architectural ceramics is enriched with a preferentially oriented rutile crystal phase, effectively improving the acid resistance of the ceramic glaze. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is an optical photograph of the blushing physically colored architectural ceramic glaze obtained in Example 1.

[0024] Figure 2 The XRD patterns of the blushed physically colored architectural ceramic glaze obtained in Example 1 are as follows: (a) before polishing; (b) after polishing.

[0025] Figure 3 These are BSEM photographs of the cross section of the blush-colored physically colored architectural ceramics obtained in Example 1: (a) and (b) are two measurement positions randomly selected on the cross section of the sample; (b-1) is a partial enlarged view of the underlayer of the effect glaze; and (b-2) is a partial enlarged view of the effect glaze.

[0026] Figure 4 BSEM photos of the surface of the blushed physically colored architectural ceramic glaze layer obtained in Example 1: (a) distribution of the crystalline phase on the glaze layer surface; (b) microscopic morphology of the crystalline phase on the glaze layer surface.

[0027] Figure 5 1. The phase separation structure (a) of the glass phase in the blushing physically colored architectural ceramic glaze layer obtained in Example 1 and the geometric size distribution diagram of the phase separation droplets (b).

[0028] Figure 6 This is an optical photograph of the architectural ceramic glaze obtained in Comparative Example 1.

[0029] Figure 7 This is an optical photograph of the architectural ceramic glaze obtained in Comparative Example 2.

[0030] Figure 8 This is an optical photograph of the architectural ceramic glaze obtained in Comparative Example 3.

[0031] Figure 9 This is an optical photograph of the architectural ceramic glaze obtained in Comparative Example 4. DETAILED DESCRIPTION

[0032] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are intended to illustrate the present invention only and are not intended to limit the present invention. Unless otherwise specified, percentages are by weight. The following is an exemplary method for preparing the blush-colored physically colored architectural ceramics of the present invention.

[0033] Prepare ceramic tile blanks. The ceramic tile blanks are ordinary brick blanks with no special requirements. Ceramic tile blanks can be prepared by dry pressing ceramic blank powder. The ceramic blank powder can be made using a conventional building ceramic formula. By way of example and not limitation, the chemical composition of the ceramic tile blank includes, by mass percentage, SiO2 67.8%; Al2O3 20%; Fe2O3 1.1%; TiO2 0.3%; CaO 0.3%; MgO 0.9%; K2O 2.9%; Na2O 1.9%; and loss on ignition 4.8%.

[0034] The green bricks are dried at a temperature and time conventional in the art. The moisture content of the green ceramic bricks after drying can be controlled to be 0.3-0.5 wt%.

[0035] A base glaze is applied to the surface of the ceramic tile and allowed to dry. The base glaze can be a standard base glaze or a cosmetic glaze, with no special requirements. The base glaze primarily serves to cover the tile, enhance its whiteness, and provide an air vent during high-temperature firing, thereby preventing glaze defects.

[0036] In some embodiments, the chemical composition of the base glaze includes, by mass percentage, SiO2 53~60%; Al2O3 25~30%; Fe2O3 0.2~0.5%; TiO2 0.1~0.2%; CaO 0.3~0.8%; MgO 0.1~0.5%; K2O 2~6%; Na2O 2~3.5%; ZrO2 4~8%; and loss on ignition 2~5%.

[0037] Any ground glaze mineral composition formula that ensures the ground glaze chemical composition falls within the above-mentioned range is suitable for use in the present invention. The ground glaze is prepared into a glaze slurry. For example, the ground glaze mineral composition, a glaze slurry dispersant, and water are ball-milled to form a ground glaze slurry. The dispersant can be any one or more of sodium tripolyphosphate, sodium carboxymethyl cellulose, sodium polyacrylate, and sodium citrate. In actual use, water can be added to the ground glaze slurry to adjust the final desired glaze slurry specific gravity.

[0038] The base glaze can be applied by pouring or spraying. Preferably, the base glaze has a specific gravity of 1.40-1.45 g / cm 3 , glaze application amount is 500~650 g / m 2 .

[0039] The bricks after base glaze application are dried.

[0040] An effect glaze is applied to the surface of the base glaze layer and dried. The chemical composition of the effect glaze includes, by mass percentage, 30-42% SiO2; 5-9% Al2O3; 30-0.1% Fe2O; 10-20% TiO2; 5-8% CaO; 0.5-1.2% MgO; 2.5-4% K2O; 0.5-1% Na2O; 0.5-1% BaO; 20-34% ZnO; 2.5-8% ZrO2; and a loss on ignition of 0.4-1.1%. The introduction of TiO2 and ZrO2 into the effect glaze promotes glass phase separation and crystallization, thereby forming a nanostructure on the surface and within the ceramic glaze layer. This nanostructure of the glass phase separation and crystallization phases achieves a characteristic response to the visible light spectrum, resulting in a purple-red iridescent decorative effect on the ceramic glaze surface. If the TiO2 and ZrO2 content is too low, the glaze crystallization ability will be weakened, which is manifested as local crystallization of the glaze layer, and the zinc silicate crystal phase is the main one. The glaze surface is transparent as a whole, with white zinc silicate crystal flowers distributed in it; if the TiO2 and ZrO2 content is too high, the glaze crystallization ability will be enhanced, and the surface will show complete crystallization of the glaze layer. The crystal phase is mainly rutile, zinc silicate, zinc titanate, and zirconium silicate. The accumulation of crystal phases can only form white spots in the glaze layer, without the physical coloring effect of a reddish halo.

[0041] In some embodiments, the mineral composition of the effect glaze includes the following raw materials in parts by mass: 40-60 parts of calcium-zinc low-temperature frit, 4-10 parts of kaolin, 16-30 parts of calcined zinc oxide, 10-20 parts of titanium dioxide, and 4-12 parts of zircon.

[0042] It should be noted that the chemical composition of the calcium-zinc low-temperature frit is not strictly limited, as long as the chemical composition of the calcium-zinc low-temperature frit, kaolin, calcined zinc oxide, titanium dioxide and zircon after mixed and ball-milled to form a slurry meets the chemical component requirements of the effect glaze of the present invention.

[0043] Preferably, the chemical composition of the calcium-zinc low-temperature frit includes, by mass percentage, SiO2 45-60%; Al2O3 5-10%; CaO 10-15%; MgO 1-3%; K2O 5-8%; Na2O 1-2%; BaO 1-2%; and ZnO 5-10%.

[0044] It should be understood that any mineral composition that makes the chemical composition of the calcium-zinc low-temperature frit fall within the above range is applicable to the present invention. As an example, the raw material composition of the calcium-zinc low-temperature frit includes: in parts by mass, 45 to 60 parts of quartz, 5 to 10 parts of calcined alumina, 17 to 28 parts of limestone, 2.1 to 6.3 parts of magnesium carbonate, 7.3 to 12 parts of potassium carbonate, 1.7 to 3.4 parts of soda ash, 1.3 to 2.6 parts of barium carbonate, and 5 to 10 parts of calcined zinc oxide. The raw materials are weighed according to the mineral composition of the calcium-zinc low-temperature frit, mixed evenly, and melted at 1320 to 1380 ° C for 2 to 4 hours to obtain a glass liquid, which is then quenched and crushed to obtain a calcium-zinc low-temperature frit. The calcium-zinc low-temperature frit can also be made by compounding commercially available ceramic frits.

[0045] In addition, it is worth noting that zinc, titanium and zirconium raw materials in effect glazes can also be willemite, anatase, aluminum titanate, zirconium oxide, etc.

[0046] The effect glaze is prepared into a glaze slurry. For example, 40-60 parts of calcium-zinc low-temperature frit, 4-10 parts of kaolin, 16-30 parts of calcined zinc oxide, 10-20 parts of titanium dioxide, 4-12 parts of zircon, 0.3-0.6 parts of a glaze dispersant, and 45-55 parts of water are ball-milled to form a glaze slurry. The dispersant can be selected from one or more of sodium tripolyphosphate, sodium carboxymethyl cellulose, sodium polyacrylate, and sodium citrate. In actual use, water can be added to the effect glaze slurry to adjust the desired specific gravity.

[0047] The effect glaze can be applied by pouring or spraying. For example, the specific gravity of the effect glaze is 1.60-1.80 g / cm 3 , glaze application amount is 600~900 g / m 2 The amount of glaze applied is crucial to the crystallization process of the effect glaze. If the amount of glaze applied is too low, the effect glaze will easily crystallize completely, resulting in a light blue glaze layer. If the amount of glaze applied is too high, it will easily make the glaze layer difficult to crystallize and vitrify completely, resulting in a milky white glaze layer.

[0048] The bricks after applying the effect glaze are dried.

[0049] The dried ceramic tiles after the effect glaze is applied are fired and edge-grinded to produce blush-colored physical colored architectural ceramics.

[0050] Firing is carried out in a roller kiln, for example, at a temperature of 1130-1160°C and a firing time of 35-60 minutes.

[0051] After firing, the effect glaze has a crystallization-amorphous-crystallization layered structure, that is, crystallization occurs first at the base glaze-effect glaze interface and on the surface of the effect glaze. That is, there is a clear crystallization layer at the base glaze-effect glaze interface and on the surface of the effect glaze, and there is an amorphous layer between the two crystallization layers, such as Figure 2 and Figure 3 As shown. The surface phase of the effect glaze is mainly composed of rutile crystal phase, while the amorphous phase has a clear phase separation structure (presenting isolated spherical droplets with a certain short-range order in distribution). The coupled superposition of Bragg scattering of the amorphous phase droplets and the coloration of rutile crystallization can lead to the formation of purple-red halo on the effect glaze surface. In addition, the crystallization of the effect glaze after firing is mainly composed of rutile, and the rutile has a clear preferred orientation, with the preferred orientation crystal plane being (110). Due to the stable chemical properties of rutile, it can effectively improve the acid resistance of the effect glaze.

[0052] The method for preparing blush-colored physical colored architectural ceramics provided by the present invention has the following beneficial effects:

[0053] (1) The present invention does not introduce coloring oxides into the effect glaze prepared. Its coloring is mainly achieved by physical coloring of the microstructure of the glaze layer. The decorative effect of this coloring method has a unique flexibility. The architectural ceramic glaze surface is slightly flushed, looming, moist like jade, and changes with the light, which is beautiful.

[0054] (2) The surface of the glaze layer in the blush-colored physical colored architectural ceramics prepared by the present invention is enriched with a rutile crystal phase with a preferred orientation, which can effectively improve the acid resistance of the ceramic glaze.

[0055] The following examples are further listed to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific numerical values ​​exemplified below.

[0056] Example 1

[0057] The specific preparation steps of a blushing physically colored architectural ceramic are as follows:

[0058] 1: Ceramic tiles are prepared by dry pressing ceramic body powder and drying. Then, a base glaze is applied to the surface of the dried tiles by spraying and drying. The chemical composition of the base glaze includes, by mass percentage, SiO2 54.5%; Al2O3 29.1%; Fe2O3 0.4%; TiO2 0.1%; CaO 0.7%; MgO 0.2%; K2O 2.4%; Na2O 3.4%; ZrO2 5.8%; and loss on ignition 3.4%. The base glaze specific gravity is controlled to be 1.42 g / cm 3 , glaze amount is 600 g / m 2 .

[0059] 2: Weigh 50 parts by mass of calcium-zinc low-temperature frit (in mass percentage, its chemical composition is: SiO2 59.3%; Al2O3 8.7%; CaO 13.2%; MgO 1.9%; K2O 6%; Na2O 1.4%; BaO 1.6%; ZnO 7.9%), 4 parts by mass of kaolin, 20 parts by mass of calcined zinc oxide, 20 parts by mass of titanium dioxide, 6 parts by mass of zircon, 0.15 parts by mass of sodium tripolyphosphate, and 0.15 parts by mass of sodium carboxymethyl cellulose, and place them together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water in a ball mill and grind them using a ball mill; then, use the ball milling time to control the glaze slurry sieve residue to 0.3-0.5wt% (325 mesh), and control the glaze slurry specific gravity to 1.80g / cm by the water content. 3 The effect glaze is thus prepared for use. The chemical composition of the effect glaze includes, by mass percentage, 33.70% SiO2; 5.75% Al2O3; 0.03% Fe2O3; 19.94% TiO2; 6.60% CaO; 0.95% MgO; 3.14% K2O; 0.69% Na2O; 0.81% BaO; 23.91% ZnO; 4.03% ZrO2; and a loss on ignition of 0.45%.

[0060] 3: Apply effect glaze on the surface of the dry ceramic tile after base glaze by pouring glaze, with a glaze amount of 600g / m 2 , followed by drying.

[0061] 4: The dried bricks with effect glaze are fired in a roller kiln at a temperature of 1145°C and a firing time of 45 minutes.

[0062] 5: After the firing is completed, edge grinding, film application and packaging are carried out to obtain the blushing physical coloring architectural ceramics.

[0063] Use an optical camera to take photos of the glaze of physically colored architectural ceramics with a reddish glow, such as Figure 1The chromaticity values ​​of the physically colored architectural ceramic glaze with a reddish halo, measured using a fully automatic colorimeter, are: L*=74.3, a*=2.9, and b*=-1.5. The red value of the glaze is greater than the blue value, resulting in an overall light purple-red hue. The glaze surface exhibits white crystals, while the outer areas of the white crystals exhibit a purple-red halo. This exhibits angular color variation (the glaze appears bluish-blue when viewed parallel to the sample, and purple-red when viewed perpendicular to the glaze surface). The glaze also exhibits a unique "immersed cloud seedling" decorative effect, resembling reddish clouds in the early morning or evening.

[0064] The phase composition of the blushed physically colored architectural ceramic glaze before and after grinding and polishing was measured by XRD (the grinding and polishing depth was about 50 μm), such as Figure 2 As shown. Before polishing, the XRD pattern of the effect glaze has obvious and sharp diffraction peaks, that is, the effect glaze is completely crystallized, and its crystalline phase composition includes TiO2 (rutile), zinc silicate, zinc titanate and zirconium silicate, with TiO2 (rutile) as the main phase, and TiO2 (rutile) has obvious preferred orientation (the preferred orientation crystal plane is (110), as shown Figure 2 After polishing, the X-ray diffraction peak intensity of the effect glaze dropped sharply (the highest peak intensity dropped from 70,000 to 2,500), and a more obvious amorphous "steamed bun peak" appeared ( Figure 2 In b), the crystalline phases are primarily zinc silicate, zinc titanate, and TiO2 (rutile), with zinc silicate and zinc titanate being the dominant phases, while the TiO2 (rutile) content is relatively low. This indicates that TiO2 (rutile) is enriched on the glaze surface, meaning that rutile crystallization occurs preferentially on the glaze surface.

[0065] Furthermore, the microstructure of the cross section of the blush-colored physical colored architectural ceramics was measured using a scanning electron microscope, such as Figure 3 As shown. The inner side of the effect glaze layer has obvious crystalline phase characteristics, mainly granular and rod-shaped / dendritic crystals; the outer microstructure of the effect glaze layer is relatively smooth and flat, without obvious crystalline phase characteristics, that is, the outer glaze layer is mainly composed of amorphous phase; and there is a clear interface between the inner crystal layer and the outer glass layer, the crystallization structure inside the interface is obvious, while there is no obvious crystallization structure outside the interface. This test result is consistent with Figure 2 The results are consistent, which proves that there is an obvious crystalline phase on the surface of the glaze layer with a blush effect, and an obvious amorphous phase on the lower side of the surface.

[0066] At the same time, the microstructure of the surface of the blushed physically colored architectural ceramic glaze layer was measured using a scanning electron microscope. Figure 4 As shown, there are a lot of point crystals on the surface of the glaze layer, and the point crystals are unevenly distributed (showing local enrichment, Figure 4In a), the color contrast of the point-shaped crystallization is brighter than that of the matrix; at the same time, the crystallization phase on the surface of the effect glaze layer is mainly granular crystallization, and also contains a small amount of needle-shaped crystals ( Figure 4 b), and there is also a distribution of glass phase between the granular crystalline phases; combined with the phase composition analysis, it can be seen that the point crystallization should be mainly TiO2 (rutile) crystalline phase.

[0067] The microstructure of the blush physical coloring effect glaze (after acid etching) was measured using a scanning electron microscope. Figure 5 As shown in Figure 2, the glass phase in the effect glaze layer exhibits a typical phase-separated structure, taking the form of spherical droplets. 2D FFT plots of the SEM images of the phase-separated droplets reveal a nearly uniform distribution of droplets with a certain degree of short-range order, consistent with the formation of amorphous photonic structural color. The scattered wavelength (λ) follows Bragg's law. Based on the geometric dimensions of the phase-separated droplets (≈207.5±30.6 nm), the Bragg scattered light wavelength is calculated to be approximately 480–630 nm when the angle between the incident light and the glaze surface is 0–90°. This indicates that the glass phase in the glaze layer can lead to the formation of structural colors in the cyan to red range. Furthermore, the extensive precipitation of rutile crystals can easily impart a light blue hue to the ceramic glaze surface. Based on the principle of three primary colors, the red structural color caused by Bragg scattering from the effect glaze glass melt and the blue-cyan crystallization of rutile in the glaze can result in the formation of a purple-red iridescence on the glaze surface.

[0068] Furthermore, the enrichment of rutile crystals on the surface of effect glazes, coupled with their chemical stability, effectively enhances their acid resistance. According to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of resistance to chemical corrosion), immersion treatment of architectural ceramic glazes in 3 vol% and 18 vol% hydrochloric acid solutions, respectively, revealed that the resulting blush-colored physically colored architectural ceramics achieved acid resistance levels of GLA and GHA (no visible corrosion on the glaze surface).

[0069] Example 2

[0070] The specific preparation steps of a blushing physically colored architectural ceramic are as follows:

[0071] 1: Ceramic green bricks are prepared by dry pressing ceramic green body powder and drying. Then, a base glaze is applied to the surface of the dried green bricks by spraying and drying. The chemical composition of the base glaze includes, by mass percentage, SiO2 54.5%; Al2O3 29.1%; Fe2O3 0.4%; TiO2 0.1%; CaO 0.7%; MgO 0.2%; K2O 2.4%; Na2O 3.4%; ZrO2 5.8%; and loss on ignition 3.4%. The specific gravity of the base glaze is controlled to be 1.40 g / cm 3, glaze amount is 500 g / m 2 .

[0072] 2: Weigh 60 parts by mass of calcium-zinc low-temperature frit (in mass percentage, its chemical composition is: SiO2 59.3%; Al2O3 8.7%; CaO 13.2%; MgO 1.9%; K2O 6%; Na2O 1.4%; BaO 1.6%; ZnO 7.9%), 10 parts by mass of kaolin, 16 parts by mass of calcined zinc oxide, 10 parts by mass of titanium dioxide, 4 parts by mass of zircon, 0.3 parts by mass of sodium tripolyphosphate, and 0.3 parts by mass of sodium polyacrylate, and place them in a ball mill together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water, and grind them in a ball mill; then, control the glaze slurry sieve residue to 0.3-0.5wt% (325 mesh) by ball milling time, and control the glaze slurry specific gravity to 1.60 g / cm by water addition. 3 The effect glaze is thus prepared and ready for use. The chemical composition of the effect glaze includes, by mass percentage, SiO2 41.94%; Al2O3 8.72%; Fe2O3 0.08%; TiO2 9.97%; CaO 7.93%; MgO 1.16%; K2O 3.93%; Na2O 0.83%; BaO 0.97%; ZnO 20.70%; ZrO2 2.69%; and loss on ignition 1.08%.

[0073] 3: Apply effect glaze on the surface of the dry ceramic tile after base glaze by pouring glaze, with a glaze amount of 900g / m 2 , followed by drying.

[0074] 4: The dried bricks with effect glaze are fired in a roller kiln at a temperature of 1160°C and a firing time of 60 min.

[0075] 5: After the firing is completed, edge grinding, film application and packaging are carried out to obtain the blushing physical coloring architectural ceramics.

[0076] The chromaticity values ​​of the blushed physically colored architectural ceramic glaze measured using a fully automatic colorimeter are: L*=82.6, a*=3.1, and b*=-1.9. The red value of the glaze is greater than the blue value, resulting in an overall pale purple-red hue and a unique "immersed cloud seedling" blushed aesthetic. According to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of chemical resistance), the acid resistance of the resulting blushed physically colored architectural ceramics reaches GLA and GHA grades.

[0077] Example 3

[0078] The specific preparation steps of a blushing physically colored architectural ceramic are as follows:

[0079] 1: Ceramic bricks are prepared by dry pressing ceramic body powder and drying. Then, a base glaze is applied to the surface of the dried brick by spraying and drying. The chemical composition of the base glaze includes, by mass percentage, SiO2 54.5%; Al2O3 29.1%; Fe2O3 0.4%; TiO2 0.1%; CaO 0.7%; MgO 0.2%; K2O 2.4%; Na2O 3.4%; ZrO2 5.8%; and loss on ignition 3.4%. The specific gravity of the base glaze is controlled to be 1.45 g / cm 3 , glaze amount is 650 g / m 2 .

[0080] 2: Weigh 45 parts by mass of calcium-zinc low-temperature frit (in mass percentage, its chemical composition is: SiO2 59.3%; Al2O3 8.7%; CaO 13.2%; MgO 1.9%; K2O 6%; Na2O 1.4%; BaO 1.6%; ZnO 7.9%), 5 parts by mass of kaolin, 30 parts by mass of calcined zinc oxide, 15 parts by mass of titanium dioxide, 5 parts by mass of zircon, 0.1 parts by mass of sodium tripolyphosphate, and 0.3 parts by mass of sodium citrate, and place them together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water in a ball mill and grind them using a ball mill; then, control the glaze slurry sieve residue to 0.3-0.5wt% (325 mesh) by ball milling time, and control the glaze slurry specific gravity to 1.70 g / cm by water addition. 3 The effect glaze is thus prepared for use. The chemical composition of the effect glaze includes, by mass percentage, 30.83% SiO2; 5.73% Al2O3; 0.04% Fe2O3; 14.96% TiO2; 5.95% CaO; 0.86% MgO; 2.87% K2O; 0.62% Na2O; 0.73% BaO; 33.51% ZnO; 3.36% ZrO2; and a loss on ignition of 0.54%.

[0081] 3: Apply effect glaze on the surface of the dry ceramic tile after base glaze by pouring glaze, with a glaze amount of 700g / m 2 , followed by drying.

[0082] 4: The dried bricks with effect glaze are fired in a roller kiln at a temperature of 1130 °C and a firing time of 35 min.

[0083] 5: After the firing is completed, edge grinding, film application and packaging are carried out to obtain the blushing physical coloring architectural ceramics.

[0084] The chromaticity values ​​of the blushed physically colored architectural ceramic glaze measured using a fully automatic colorimeter are: L*=69.8, a*=2.1, and b*=-0.9. The red value of the glaze is greater than the blue value, resulting in an overall pale purple-red hue and a unique "immersed cloud seedling" blushed aesthetic. According to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of chemical resistance), the acid resistance of the resulting blushed physically colored architectural ceramics reaches GLA and GHA grades.

[0085] Example 4

[0086] The specific preparation steps of a blushing physically colored architectural ceramic are as follows:

[0087] 1: Ceramic bricks are prepared by dry pressing ceramic body powder and drying. Then, a base glaze is applied to the surface of the dried brick by spraying and drying. The chemical composition of the base glaze includes, by mass percentage, SiO2 54.5%; Al2O3 29.1%; Fe2O3 0.4%; TiO2 0.1%; CaO 0.7%; MgO 0.2%; K2O 2.4%; Na2O 3.4%; ZrO2 5.8%; and loss on ignition 3.4%. The specific gravity of the base glaze is controlled to be 1.43 g / cm 3 , glaze amount is 620 g / m 2 .

[0088] 2: Weigh 40 parts by mass of calcium-zinc low-temperature frit (in mass percentage, its chemical composition is: SiO2 59.3%; Al2O3 8.7%; CaO 13.2%; MgO 1.9%; K2O 6%; Na2O 1.4%; BaO 1.6%; ZnO 7.9%), 5 parts by mass of kaolin, 25 parts by mass of calcined zinc oxide, 18 parts by mass of titanium dioxide, 12 parts by mass of zircon and 0.5 parts by mass of sodium tripolyphosphate, and place them together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water in a ball mill and grind them using a ball mill; then, control the glaze slurry sieve residue to 0.3-0.5wt% (325 mesh) by ball milling time, and control the glaze slurry specific gravity to 1.65 g / cm by water addition. 3 The effect glaze is thus prepared for use. The chemical composition of the effect glaze includes, by mass percentage, SiO2 30.24%; Al2O3 5.23%; Fe2O3 0.04%; TiO2 17.95%; CaO 5.29%; MgO 0.77%; K2O 2.57%; Na2O 0.55%; BaO 0.65%; ZnO 28.12%; ZrO2 8.06%; and a loss on ignition of 0.53%.

[0089] 3: Use the spray glaze method to apply effect glaze on the surface of the dry ceramic tile after the base glaze is applied. The glaze amount is 750g / m 2 , followed by drying.

[0090] 4: The dried bricks with effect glaze are fired in a roller kiln at a temperature of 1140 °C and a firing time of 50 min.

[0091] 5: After the firing is completed, edge grinding, film application and packaging are carried out to obtain the blushing physical coloring architectural ceramics.

[0092] The chromaticity values ​​of the blushed physically colored architectural ceramic glaze measured using a fully automatic colorimeter are: L*=69.8, a*=4.3, and b*=-1.6. The red value of the glaze is greater than the blue value, resulting in an overall pale purple-red hue and a unique "immersed cloud seedling" blushed aesthetic. According to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of chemical resistance), the acid resistance of the resulting blushed physically colored architectural ceramics reaches GLA and GHA grades.

[0093] Comparative Example 1

[0094] The technical solutions of Comparative Example 1 and Example 2 are basically the same, with the main difference being that the amount of effect glaze applied in Comparative Example 1 is greater than that in Example 2. The specific gravity of the effect glaze in Comparative Example 1 is controlled to be 1.60 g / cm 3 The effect glaze is applied on the surface of the dry ceramic tile after the base glaze is applied by pouring glaze, and the glaze amount is 1000 g / m 2 .

[0095] Use an optical camera to take photos of the glaze surface of the prepared architectural ceramics, such as Figure 6 The chromaticity values ​​of the blushed physically colored architectural ceramic glaze measured using a fully automatic colorimeter are: L*=85.6, a*=1.3, b*=4.1. The glaze layer is opaque and milky, with a yellow value greater than a blue value. The overall appearance is milky white (yellowish), with no noticeable decorative effect.

[0096] Comparative Example 2

[0097] The technical solutions of Comparative Example 2 are basically the same as those of Example 2, with the main difference being that the amount of effect glaze applied in Comparative Example 2 is less than that in Example 2. The specific gravity of the effect glaze in Comparative Example 2 is controlled to be 1.60 g / cm 3 The effect glaze is applied on the surface of the dry ceramic tile after the base glaze is applied by pouring glaze, and the glaze amount is 500 g / m 2 .

[0098] Use an optical camera to take photos of the glaze surface of the prepared architectural ceramics, such as Figure 7The chromaticity values ​​of the blushed physically colored architectural ceramic glaze measured using a fully automatic colorimeter are: L*=71.0, a*=2.0, b*=-3.4. The glaze layer is matte, the ceramic glaze color is light blue, and the overall color is relatively simple.

[0099] Comparative Example 3

[0100] The technical solutions of Comparative Example 3 and Example 1 are basically the same, with the main difference being that the TiO2 and ZrO2 contents of the effect glaze in Comparative Example 3 are lower than those in Example 1. In Comparative Example 3, 60 parts by mass of calcium-zinc low-temperature frit, 10 parts by mass of kaolin, 23 parts by mass of calcined zinc oxide, 5 parts by mass of titanium dioxide, 2 parts by mass of zircon, 0.15 parts by mass of sodium tripolyphosphate, and 0.15 parts by mass of sodium carboxymethyl cellulose are weighed respectively, and placed in a ball mill together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water, and ground using a ball mill; then, the ball milling time is used to control the sieve residue of the glaze slurry to be 0.3-0.5wt% (325 mesh), and the water content is used to control the specific gravity of the glaze slurry to be 1.60 g / cm 3 The effect glaze is thus prepared for use. The chemical composition of the effect glaze includes, by mass percentage, SiO2 41.28%; Al2O3 8.72%; Fe2O3 0.08%; TiO2 4.99%; CaO 7.93%; MgO 1.16%; K2O 3.93%; Na2O 0.83%; BaO 0.97%; ZnO 27.69%; ZrO2 1.34%; and loss on ignition 1.08%.

[0101] Use an optical camera to take photos of the glaze surface of the prepared architectural ceramics, such as Figure 8 As shown, the ceramic glaze surface exhibits partial crystallization, with white zinc silicate crystals precipitating within the transparent glaze layer, without any physical coloring effect that would suggest a reddish hue. Furthermore, according to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of resistance to chemical corrosion), the resulting architectural ceramics meet GLC and GHB acid resistance standards (visible corrosion damage is present at the white crystals).

[0102] Comparative Example 4

[0103] The technical solutions of Comparative Example 4 and Example 1 are basically the same, with the main difference being that the TiO2 and ZrO2 contents of the effect glaze in Comparative Example 4 are higher than those in Example 1. In Comparative Example 4, 40 parts by mass of calcium-zinc low-temperature frit, 5 parts by mass of kaolin, 18 parts by mass of calcined zinc oxide, 23 parts by mass of titanium dioxide, 14 parts by mass of zircon, 0.15 parts by mass of sodium tripolyphosphate, and 0.15 parts by mass of sodium carboxymethyl cellulose are weighed respectively, and placed in a ball mill together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water, and ground using a ball mill; then, the ball milling time is used to control the sieve residue of the glaze slurry to be 0.3-0.5wt% (325 mesh), and the water content is used to control the specific gravity of the glaze slurry to be 1.60 g / cm 3 The effect glaze is thus prepared for use. The chemical composition of the effect glaze includes, by mass percentage, SiO2 30.90%; Al2O3 5.23%; Fe2O3 0.04%; TiO2 22.93%; CaO 5.29%; MgO 0.77%; K2O 2.57%; Na2O 0.55%; BaO 0.65%; ZnO 21.13%; ZrO2 9.41%; and loss on ignition 0.53%.

[0104] Use an optical camera to take photos of the glaze surface of the prepared architectural ceramics, such as Figure 9 As shown, the ceramic glaze surface is crystallized as a whole, and the crystal phase accumulates in the glaze layer to form white spots, without the physical coloring effect of a reddish glow.

Claims

1. A method for preparing blush-colored physically colored architectural ceramics, characterized in that: The preparation method comprises the following steps: Step (1) applying a base glaze on the surface of the ceramic tile and performing a drying process; Step (2) applying effect glaze on the surface of the dried ceramic tile blank after applying the base glaze, and drying the surface; the raw material composition of the effect glaze includes: in parts by mass, 40-60 parts of calcium zinc low-temperature frit, 4-10 parts of kaolin, 16-30 parts of calcined zinc oxide, 10-20 parts of titanium dioxide, and 4-12 parts of zircon; wherein the chemical composition of the calcium zinc low-temperature frit includes: in mass percentage, SiO2 45-60%; Al2O3 5-10%; CaO 10-15%; MgO 1-3%; K2O 5-8%; Na2O 1-2%; BaO 1-2%; ZnO 5-10%; the chemical composition of the effect glaze includes: in mass percentage, SiO2 30-42%; Al2O3 5-9%; TiO2 10-20%; CaO 5-8%; MgO 0.5-1.2%; K2O 2.5~4%; Na2O 0.5~1%; BaO 0.5~1%; ZnO 20~34%; ZrO2 2.5~8%; loss on ignition 0.4~1.1%; the specific gravity of the effect glaze is 1.60~1.80 g / cm 3 , glaze application amount is 600~900 g / m 2 ; Step (3) The dried ceramic tile blanks after applying the effect glaze are fired and edge-grinded to obtain blush-colored physical colored architectural ceramics.

2. The preparation method according to claim 1, wherein The chemical composition of the base glaze includes, by mass percentage, SiO2 53-60%; Al2O3 25-30%; Fe2O3 0.2-0.5%; TiO2 0.1-0.2%; CaO 0.3-0.8%; MgO 0.1-0.5%; K2O 2-6%; Na2O 2-3.5%; ZrO2 4-8%; and loss on ignition 2-5%.

3. The preparation method according to claim 1, wherein The specific gravity of the base glaze is 1.40-1.45 g / cm 3 , glaze application amount is 500~650 g / m 2 The base glaze is applied by pouring or spraying.

4. The preparation method according to claim 1, characterized in that The effect glaze is applied by pouring glaze or spraying glaze.

5. The preparation method according to claim 1, wherein The firing temperature is 1130~1160℃, and the firing time is 35~60 min.

6. The preparation method according to claim 1, characterized in that The fired effect glaze has a layered structure of crystallization-amorphous-crystallization, and crystallization occurs preferentially at the base glaze-effect glaze interface and on the surface of the effect glaze.

7. The preparation method according to claim 6, characterized in that The amorphous phase has a distinct phase separation structure, appears as isolated spherical droplets, and has a short-range order in distribution.

8. The preparation method according to claim 6, characterized in that After firing, the surface crystallization phase of the glaze is mainly rutile crystal phase, and the rutile has obvious preferred orientation, and the preferred orientation crystal plane is 110.

9. The preparation method according to claim 8, characterized in that The coupled superposition of Bragg scattering of amorphous phase droplets and rutile crystallization coloring leads to the formation of purple-red iridescence on the effect glaze surface.

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