Preparation method of reddish halo physical coloring building ceramic

Abstract

The invention belongs to the technical field of surface decoration of architectural ceramics, and particularly relates to a preparation method of a reddish halo physical coloring architectural ceramic. The preparation method comprises the following steps: (1) applying ground glaze to the surface of a ceramic tile blank, and drying; (2) effect glaze is applied to the surface of the dried ceramic tile blank after the ground glaze is applied, and drying treatment is carried out; and (3) carrying out firing and edging treatment on the dried ceramic tile blank to which the effect glaze is applied, so as to obtain the reddish halo physical coloring building ceramic. According to the invention, by regulating and controlling the split-phase and devitrification properties of the architectural ceramic glaze layer, the preparation of the pan-halo architectural ceramic is realized by utilizing glass-devitrification composite physical coloring.

Description

Technical Field

[0001] The present invention belongs to the technical field of surface decoration of building ceramics, and particularly relates to a preparation method of a physical coloring building ceramics with a red halo. Background Art

[0002] With the continuous development of China's national economy and the increasing improvement of people's living standards, the aesthetic and appreciation abilities of consumers have also been continuously improved. As a result, consumers pay more attention to obtaining aesthetic enjoyment from the building decoration environment. Therefore, people's requirements for the decoration of building ceramic products are gradually increasing, and they pay more attention to the individuality and decoration effect of building ceramics. At present, building ceramics mainly use inkjet printing to achieve colorization and patterning, and it is mainly chemical color (pigment color), that is, the color is achieved by the selective absorption of light by the colorants / pigments in the ink. The controllability of chemical color is relatively strong, and it is easy to achieve large-scale replication of products; however, the color rendering effect is single, lacking the flexibility of change.

[0003] The structural color technology, also known as physical coloring, does not contain any coloring chemical elements. It mainly presents colors by selectively reflecting, scattering, interfering or diffracting light by the microstructure of the material. Compared with chemical color, the structural color is only related to the microstructure of the material, and its color durability is significantly better than that of chemical color; moreover, there is no need to use chemical colorants, and its coloring method is more environmentally friendly; in addition, the structural color is more sensitive to light, and in most cases has angle-dependent color change or iridescence. For example, a large number of structural colors are contained in Jun porcelain glaze, Tianmu glaze, celadon glaze, etc., which can bring people strange and wonderful light and color perceptions, thereby improving the decoration effect of ceramic products.

[0004] In view of the special decorative effect of physical coloring, a series of research and development work on physical coloring technology for architectural ceramics has been carried out currently. The patents with patent publication number CN106431504A, patent announcement number CN103288492B, and patent publication number CN109180220A deposit photonic crystal films on the surface of the glaze layer of the architectural ceramic sintered body, and use the periodic arrangement of photonic crystals to achieve physical coloring. However, this method has a relatively low heat treatment temperature (500 - 900 °C) for the photonic crystal film layer, which easily leads to poor mechanical properties and durability of the film layer, and the secondary sintering heat treatment will increase the manufacturing cost of architectural ceramics and reduce production efficiency. The patents with patent publication number CN117843395A and patent announcement number CN221777980U use femtosecond laser equipment to finely process the glaze layer or coated film layer of architectural ceramics, and use the prepared periodically arranged micro-nano structures to achieve physical coloring. However, this method has high requirements for equipment and is difficult to apply industrially. In addition, the patents with patent publication number CN105712630A and patent publication number CN119350063A achieve physical coloring by means of ceramic glaze layer formula and structure design, using the spectral response characteristics of the precipitated crystalline phase. However, these 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] "Showing a faint purple blush" refers to the phenomenon that the ceramic product shows a "blush" of local glaze color turning purplish red under light, which is common in traditional Ru porcelain and is also one of the important characteristics for Ru porcelain identification. The local glaze surface slightly shows a faint purple blush, changing with the light, appearing and disappearing faintly, moist like jade, extremely beautiful, which can greatly enhance the decorative effect of the ceramic product. However, the formation mechanism of the phenomenon of Ru porcelain showing a faint purple blush is not yet fully understood at present, and the high-temperature reduction firing of traditional Ru porcelain is also difficult to apply to the manufacture of architectural ceramics, so there is no research and development of purple blush color architectural ceramic products at home and abroad; moreover, the above physical coloring technologies cannot achieve the decorative effect of architectural ceramics showing a faint purple blush. Summary of the Invention

[0006] In view of this, the present invention realizes the preparation of purple blush architectural ceramics by regulating the phase separation and crystallization properties of the glaze layer of architectural ceramics and using the composite physical coloring of glass-crystallization. The present invention adopts the following technical solutions to achieve the above purpose: The present invention provides a method for preparing purple blush physical coloring architectural ceramics. The preparation method includes the following steps: Step (1) Apply a base glaze on the surface of the ceramic tile blank and perform a drying treatment; Step (2) Apply an effect glaze on the surface of the dried ceramic tile blank after applying the base glaze and perform a drying treatment; Step (3): The dried ceramic tile blank applied with the effect glaze is fired and edge-ground to obtain the physical coloration building ceramics with a red halo.

[0007] Preferably, the chemical composition of the base glaze includes: by mass percentage, SiO 2 53 - 60%; Al 2 O 3 25 - 30%; Fe 2 O 3 0.2 - 0.5%; TiO 2 0.1 - 0.2%; CaO 0.3 - 0.8%; MgO 0.1 - 0.5%; K 2 O 2 - 6%; Na 2 O 2 - 3.5%; ZrO 2 4 - 8%; loss on ignition 2 - 5%.

[0008] Preferably, the specific gravity of the base glaze is 1.40 - 1.45 g / cm 3 , and the glaze application amount is 500 - 650 g / m 2 ; the application method of the base glaze is glaze pouring or spraying.

[0009] Preferably, the chemical composition of the effect glaze includes: by mass percentage, SiO 2 30 - 42%; Al 2 O 3 5 - 9%; TiO 2 10 - 20%; CaO 5 - 8%; MgO 0.5 - 1.2%; K 2 O 2.5 - 4%; Na 2 O 0.5 - 1%; BaO 0.5 - 1%; ZnO 20 - 34%; ZrO 2 2.5 - 8%; loss on ignition 0.4 - 1.1%.

[0010] Preferably, the mineral composition of the effect glaze includes: by mass parts, 40 - 60 parts of calcium-zinc-based 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; wherein, the chemical composition of the calcium-zinc-based low-temperature frit includes: by mass percentage, SiO 2 45 - 60%; Al 2 O 3 5 - 10%; CaO 10 - 15%; MgO 1 - 3%; K 2 O 5 - 8%; Na 2 O 1 - 2%; BaO 1 - 2%; ZnO 5 - 10%.

[0011] Preferably, the specific gravity of the effect glaze is 1.60 - 1.80 g / cm 3 , and the glazing amount is 600 - 900 g / m 2 ; the application method of the effect glaze is pouring glaze or spraying glaze.

[0012] Preferably, the firing temperature is 1130 - 1160 °C, and the firing time is 35 - 60 min.

[0013] Preferably, the fired effect glaze has a laminated structure of crystallization - amorphous - crystallization, and crystallization preferentially occurs at the interface between the base glaze and the effect glaze and on the surface of the effect glaze.

[0014] Preferably, the amorphous phase has an obvious phase - separated structure, presenting isolated spherical droplets, and the distribution has short - range order.

[0015] Preferably, the crystalline phase of the crystals on the surface of the fired effect glaze is mainly rutile, and the rutile has an obvious preferred orientation, and the preferred - orientation crystal plane is (110).

[0016] Preferably, the coupled superposition of the Bragg scattering of the amorphous - phase droplets and the coloring of rutile crystallization promotes the formation of the purplish - red halo color on the glaze surface of the effect glaze.

[0017] The present invention has the following beneficial effects: Based on the glaze layer formula design of building ceramics, by using the crystallization ability of the effect glaze to regulate, a ceramic glaze layer with a laminated structure of crystallization - amorphous - crystallization can be prepared. By using the coupled superposition of the Bragg scattering of the amorphous phase and the coloring of TiO 2 (rutile) crystallization, a purplish - red halo color can be formed on the ceramic glaze surface, which can improve the decorative effect of building ceramic products. Moreover, in the physically - colored building ceramics with a purplish - red halo prepared by the present invention, the surface of the glaze layer is enriched with rutile crystalline phases with preferred orientation, which can effectively improve the acid resistance of the ceramic glaze. Description of the Drawings

[0018] Figure 1 is the optical photograph of the glaze surface of the physically - colored building ceramics with a purplish - red halo prepared in Example 1.

[0019] Figure 2 is the XRD pattern of the glaze surface of the physically - colored building ceramics with a purplish - red halo prepared in Example 1: (a) before grinding and polishing; (b) after grinding and polishing.

[0020] Figure 3 is the BSEM photograph of the cross - section of the physically - colored building ceramics with a purplish - red halo prepared in Example 1: (a) and (b) are two randomly selected measurement positions at the cross - section of the specimen; (b - 1) is the partial enlarged view of the lower layer of the effect glaze; (b - 2) is the partial enlarged view of the effect glaze.

[0021] Figure 4 It is the BSEM photograph of the surface of the physical coloring architectural ceramic glaze layer with a blush obtained in Example 1: (a) the distribution of the crystalline phase on the glaze layer surface; (b) the microscopic morphology of the crystalline phase on the glaze layer surface.

[0022] Figure 5 It is the phase separation structure (a) of the glass phase in the physical coloring architectural ceramic glaze layer with a blush obtained in Example 1 and the geometric size distribution diagram (b) of its phase separation droplets.

[0023] Figure 6 It is the optical photograph of the architectural ceramic glaze surface obtained in Comparative Example 1.

[0024] Figure 7 It is the optical photograph of the architectural ceramic glaze surface obtained in Comparative Example 2.

[0025] Figure 8 It is the optical photograph of the architectural ceramic glaze surface obtained in Comparative Example 3.

[0026] Figure 9 It is the optical photograph of the architectural ceramic glaze surface obtained in Comparative Example 4. Specific Embodiments

[0027] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and do not limit the present invention. Without specific description, the percentage refers to the mass percentage. The following exemplarily illustrates the preparation method of the physical coloring architectural ceramic with a blush according to the present invention.

[0028] Prepare the ceramic tile blank. The ceramic tile blank is a common tile blank without special requirements. The ceramic tile blank can be prepared by dry pressing the ceramic body powder. The ceramic body powder can adopt a conventional architectural ceramic formula. As an example but not limited to this, the chemical composition of the ceramic tile blank includes: by mass percentage, SiO 2 67.8%; Al 2 O 3 20%; Fe 2 O 3 1.1%; TiO 2 0.3%; CaO 0.3%; MgO 0.9%; K 2 O 2.9%; Na 2 O 1.9%; loss on ignition 4.8%.

[0029] Perform a drying treatment on the tile blank. The drying temperature and drying time are conventional settings in the art. After the drying treatment, the moisture content of the ceramic tile blank can be controlled to 0.3 - 0.5 wt%.

[0030] Apply a base glaze on the surface of the ceramic tile blank and conduct a drying treatment. The base glaze is a conventional base glaze or a slip, with no special requirements. The base glaze mainly serves to cover the blank, enhance the whiteness of the tile blank, and provide an exhaust channel during the high-temperature firing process of the blank, which can avoid the generation of glaze defects.

[0031] In some embodiments, the chemical composition of the base glaze includes: by mass percentage, SiO 2 53 - 60%; Al 2 O 3 25 - 30%; Fe 2 O 3 0.2 - 0.5%; TiO 2 0.1 - 0.2%; CaO 0.3 - 0.8%; MgO 0.1 - 0.5%; K 2 O 2 - 6%; Na 2 O 2 - 3.5%; ZrO 2 4 - 8%; loss on ignition 2 - 5%.

[0032] Any base glaze mineral composition formula that makes the chemical composition of the base glaze fall within the above range is applicable to the present invention. Prepare the base glaze into a glaze slurry. For example, ball mill the base glaze mineral composition, glaze slurry dispersant, and water evenly to prepare the base glaze slurry. The dispersant can be any one or more of sodium tripolyphosphate, sodium carboxymethylcellulose, sodium polyacrylate, and sodium citrate. During actual use, water can be added to the base glaze slurry to adjust the specific gravity of the final required glaze slurry.

[0033] The application method of the base glaze can be glaze pouring or spraying. Preferably, the specific gravity of the base glaze is 1.40 - 1.45 g / cm 3 , and the glaze application amount is 500 - 650 g / m 2 .

[0034] Conduct a drying treatment on the tile blank after applying the base glaze.

[0035] Apply an effect glaze on the surface of the base glaze layer and conduct a drying treatment. The chemical composition of the effect glaze includes: by mass percentage, SiO 2 30 - 42%; Al 2 O 3 5 - 9%; Fe 2 O 3 0 - 0.1%; TiO 2 10 - 20%; CaO 5 - 8%; MgO 0.5 - 1.2%; K 2 O 2.5 - 4%; Na 2 O 0.5 - 1%; BaO 0.5 - 1%; ZnO 20 - 34%; ZrO 22.5 - 8%; loss on ignition 0.4 - 1.1%. TiO is introduced into the effect glaze. 2 , ZrO 2 promotes glass phase separation and crystallization, so that nano - microstructures can be formed on the surface and inside of the ceramic glaze layer. The nano - microstructures of the glass phase separation and crystallization phases are used to achieve their characteristic response to the visible light spectrum, so that a purplish - red halo decoration effect can be formed on the ceramic glaze surface. TiO 2 , ZrO 2 If the content is too low, the crystallization ability of the effect glaze weakens, manifested as local crystallization of the glaze layer, mainly with zinc silicate crystal phase, and the overall glaze surface is transparent, with white zinc silicate crystal flowers distributed in it; while TiO 2 , ZrO 2 If the content is too high, the crystallization ability of the effect glaze increases, and the surface is completely crystallized in the glaze layer. The crystal phases are 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 red halo.

[0036] 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 - based 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.

[0037] It should be noted that the chemical composition of the calcium - zinc - based low - temperature frit is not strictly limited, as long as the chemical composition after mixing and ball - milling the calcium - zinc - based low - temperature frit, kaolin, calcined zinc oxide, titanium dioxide, and zircon meets the chemical component requirements of the effect glaze of the present invention.

[0038] Preferably, the chemical composition of the calcium - zinc - based low - temperature frit includes: by mass percentage, SiO 2 45 - 60%; Al 2 O 3 5 - 10%; CaO 10 - 15%; MgO 1 - 3%; K 2 O 5 - 8%; Na 2 O 1 - 2%; BaO 1 - 2%; ZnO 5 - 10%.

[0039] It should be understood that any mineral composition that makes the chemical composition of the calcium-zinc-based 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-based low-temperature frit includes: 45-60 parts by mass of quartz, 5-10 parts of calcined alumina, 17-28 parts of limestone, 2.1-6.3 parts of magnesium carbonate, 7.3-12 parts of potassium carbonate, 1.7-3.4 parts of soda ash, 1.3-2.6 parts of barium carbonate, and 5-10 parts of calcined zinc oxide. Weigh each raw material according to the mineral composition of the calcium-zinc-based low-temperature frit, mix them evenly, and then melt them at 1320-1380 °C for 2-4 hours to obtain a glass melt. Then, water-quench and crush the glass melt to obtain the calcium-zinc-based low-temperature frit. The calcium-zinc-based low-temperature frit can also be prepared by compounding commercially available ceramic frits.

[0040] In addition, it is worth noting that zinc, titanium, and zirconium-based raw materials in the effect glaze can also be selected from willemite, anatase, aluminum titanate, zirconia, etc.

[0041] Prepare the effect glaze into a glaze slurry. For example, 40-60 parts of the calcium-zinc-based 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 slurry dispersant, and 45-55 parts of water are ball-milled evenly to prepare the effect glaze slurry. Any one or more of sodium tripolyphosphate, sodium carboxymethylcellulose, sodium polyacrylate, and sodium citrate can be selected as the above dispersant. When actually used, water can be added to the effect glaze slurry to adjust the specific gravity of the finally required glaze slurry.

[0042] The application method of the effect glaze can be pouring glaze or spraying glaze. For example, the specific gravity of the effect glaze is 1.60-1.80 g / cm 3 , and the glaze application amount is 600-900 g / m 2 . The glaze application amount is crucial for the crystallization process of the effect glaze. If the glaze application amount is too low, it is easy to cause the complete crystallization of the effect glaze, resulting in a light blue color of the glaze layer; if the glaze application amount is too high, it is easy to cause difficulty in crystallization of the glaze layer and complete vitrification, resulting in a milky white color of the glaze layer.

[0043] Dry the brick blank after applying the effect glaze.

[0044] The dried ceramic brick blank after applying the effect glaze is fired and edge-ground to obtain a physically colored building ceramic with a red halo.

[0045] Firing is carried out using a roller hearth kiln. For example, the firing temperature is 1130-1160 °C, and the firing time is 35-60 min.

[0046] The fired effect glaze has a crystalline - amorphous - crystalline laminated structure, that is, crystallization preferentially occurs at the interface between the base glaze and the effect glaze and on the surface of the effect glaze. That is, obvious crystalline layers exist at both the interface between the base glaze and the effect glaze and on the surface of the effect glaze, and there is an amorphous layer between the two crystalline layers, as Figure 2 and Figure 3 shown. And the main phase on the surface of the effect glaze is the rutile crystalline phase, and the amorphous phase has an obvious phase - separation structure (showing isolated spherical droplets with a certain short - range order in distribution); the coupled superposition of the Bragg scattering of the amorphous phase droplets and the coloring of rutile crystallization can lead to the formation of a purplish - red iridescence on the surface of the effect glaze. In addition, the crystallization on the surface of the fired effect glaze is mainly rutile, and rutile has an obvious preferred orientation, and the preferred - orientation crystal plane is (110); due to the stable chemical properties of rutile, it can effectively improve the acid - resistance of the effect glaze.

[0047] The preparation method of the physical - coloring architectural ceramics with a purplish - red halo provided by the present invention has the following beneficial effects: (1) No coloring oxides are introduced into the prepared effect glaze of the present invention, and its coloration mainly utilizes the physical coloring of the glaze - layer microstructure. The decorative effect of this coloring method has unique flexibility. The surface of the architectural ceramic glaze slightly shows a purplish - red halo, looming, moist like jade, changing with light, and extremely beautiful.

[0048] (2) In the physical - coloring architectural ceramics with a purplish - red halo prepared by the present invention, the surface of the glaze layer is enriched with rutile crystalline phase with preferred orientation, which can effectively improve the acid - resistance of the ceramic glaze.

[0049] The following further lists examples 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 construed as limiting the protection scope 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 protection scope of the present invention. The specific process parameters and the like in the following examples are also only an example within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, rather than being limited to the specific values in the following examples.

[0050] Example 1

[0051] The specific preparation steps of a physical - coloring architectural ceramics with a purplish - red halo are as follows: 1: Prepare a ceramic tile blank by dry - pressing the ceramic body powder and conduct a drying treatment. Then, use the spraying method to apply a base glaze on the surface of the dried blank and conduct a drying treatment. The chemical composition of the base glaze includes: by mass percentage, SiO 2 54.5%; Al 2 O 3 29.1%; Fe 2 O 30.4%; TiO 2 0.1%; CaO 0.7%; MgO 0.2%; K 2 O 2.4%; Na 2 O 3.4%; ZrO 2 5.8%; Loss on ignition 3.4%. The specific gravity of the base glaze is controlled to be 1.42 g / cm 3 , and the glaze application amount is 600 g / m 2 .

[0052] 2: Weigh 50 parts by mass of a calcium-zinc-based low-temperature frit (in terms of mass percentage, its chemical composition is: SiO 2 59.3%; Al 2 O 3 8.7%; CaO 13.2%; MgO 1.9%; K 2 O 6%; Na 2 O 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, as well as 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 tank, and use a ball mill for grinding; then, control the sieve residue of the glaze slurry to be 0.3 - 0.5 wt% (325 mesh) by the ball milling time, and control the specific gravity of the glaze slurry to be 1.80 g / cm 3 , and thus the effect glaze can be prepared for standby. The chemical composition of the effect glaze includes: in terms of mass percentage, SiO 2 33.70%; Al 2 O 3 5.75%; Fe 2 O 3 0.03%; TiO 2 19.94%; CaO 6.60%; MgO 0.95%; K 2 O 3.14%; Na 2 O 0.69%; BaO 0.81%; ZnO 23.91%; ZrO 2 4.03%; Loss on ignition 0.45%.

[0053] 3: Apply the effect glaze on the surface of the dried ceramic tile blank with the base glaze by the method of pouring glaze, and the glaze application amount is 600 g / m 2 , and then carry out drying treatment.

[0054] 4: Use a roller hearth kiln to carry out firing treatment on the dried tile blank with the effect glaze applied. The firing temperature is 1145 °C and the firing time is 45 min.

[0055] 5: After firing is completed, edge grinding, film pasting, and packing are carried out to obtain the physically colored architectural ceramics with a purple halo.

[0056] The glaze surface photo of the physically colored architectural ceramics with a purple halo is taken by an optical camera, as Figure 1 shown. The chromaticity values of the glaze surface of the physically colored architectural ceramics with a purple halo are measured by a full-automatic color difference meter as: L* = 74.3, a* = 2.9, b* = -1.5. The chromaticity red value of the ceramic glaze is greater than the blue value, presenting a light purplish red overall; and white crystallization appears on the glaze layer surface, while a purple-red iridescence appears outside the white crystallization area, with the characteristic of color change with viewing angle (when observed parallel to the specimen, the glaze surface is cyan-blue; when observed perpendicular to the glaze surface, the glaze surface is purple-red), and at the same time has a unique "soaking cloud seedling" decorative effect (resembling the red-tinged clouds in the early morning or evening).

[0057] The phase composition of the glaze surface of the physically colored architectural ceramics with a purple halo before and after grinding and polishing is measured by XRD (the grinding and polishing depth is about 50 μm), as Figure 2 shown. Before grinding and polishing, there are obvious and sharp diffraction peaks in the XRD pattern of the effect glaze, that is, the effect glaze is completely crystallized, and its crystalline phase composition includes TiO 2 (rutile), zinc silicate, zinc titanate, and zirconium silicate, with TiO 2 (rutile) as the main phase, and TiO 2 (rutile) has obvious preferred orientation (the preferred orientation crystal plane is (110), as Figure 2 shown in a of). After grinding and polishing, the X-ray diffraction peak intensity of the effect glaze decreases sharply (the highest peak intensity drops from 70000 to 2500), and there appears an obvious amorphous "bread-like peak" ( Figure 2 shown in b of), and its crystalline phase is mainly zinc silicate, zinc titanate, and TiO 2 (rutile), and is mainly composed of zinc silicate and zinc titanate phases, and the content of TiO 2 (rutile) is low. It can be seen from this that there is enrichment of TiO 2 (rutile) on the glaze layer surface, that is, the crystallization and precipitation of rutile occur preferentially on the glaze layer surface.

[0058] Furthermore, the microstructure of the cross-section of the physically colored architectural ceramics with a purple halo is measured by a scanning electron microscope, as Figure 3 shown. The inner side of the effect glaze layer has obvious crystalline phase characteristics, mainly granular and rod / dendritic crystals; the microstructure on the outer side of the effect glaze layer is relatively smooth and flat, and no obvious crystalline phase characteristics are seen, that is, the outer glaze layer is mainly amorphous phase; and there is an obvious interface between the inner crystalline layer and the outer glass layer, with obvious crystallization structure on the inner side of the interface, while there is no obvious crystallization structure on the outer side of the interface. This test result is consistent with Figure 2Consistent, it can be confirmed that there are obvious crystallized phases on the surface layer of the glaze with a blush effect, and obvious amorphous phases exist on the lower side of the surface layer.

[0059] At the same time, the microstructure of the surface of the glaze of the blush physical coloring architectural ceramics was measured by scanning electron microscopy, such as Figure 4 shown. There are a large number of dot-like crystallizations on the surface of the glaze, and the dot-like crystallizations are unevenly distributed (showing local enrichment, Figure 4 a in), and the color contrast of the dot-like crystallizations is brighter than that of the matrix; at the same time, the crystallization phase on the surface of the effect glaze is mainly granular crystals, and there are also a small number of needle-like crystals ( Figure 4 b in), and there is also a distribution of glass phase between the granular crystal phases; combined with the analysis of the phase composition, it can be known that the dot-like crystallizations should be mainly TiO 2 (rutile) crystal phase.

[0060] The microstructure in the blush physical coloring effect glaze (after acid etching treatment) was measured by scanning electron microscopy, such as Figure 5 shown. The glass phase in the effect glaze has a typical phase separation structure, showing a spherical droplet-like phase separation structure; the 2D FFT diagram of the SEM photo of the phase separation droplets shows that the phase separation droplets are basically evenly distributed, and the distribution characteristics have a certain short-range order, meeting the formation conditions of amorphous photonic structural color. The scattered wavelength (λ) follows the Bragg law. According to the geometric size of the phase separation droplets (≈207.5 ± 30.6 nm), it can be calculated that when the incident light and the glaze surface form an angle of 0 - 90°, the Bragg scattering light wavelength is about 480 - 630 nm, that is, the glass phase of the glaze layer can lead to the formation of structural color in the range from cyan to red. In addition, the large precipitation of rutile crystal phase easily makes the ceramic glaze surface show a light blue color. Based on the principle of the three primary colors, due to the superposition effect of the red structural color caused by the Bragg scattering of the effect glaze glass melt and the blue-cyan crystallization of rutile in the glaze, it can lead to the formation of a purplish-red blush on the glaze surface.

[0061] In addition, because the rutile crystal phase is enriched on the surface of the effect glaze, and rutile has stable chemical properties, it can effectively improve the acid resistance of the effect glaze. According to GB / T 3810.13 - 2016 (Test methods for ceramic tiles - Part 13: Determination of chemical corrosion resistance), the surface of the architectural ceramic glaze was soaked respectively with 3 vol% and 18 vol% hydrochloric acid solutions, and the acid resistance of the prepared blush physical coloring architectural ceramics was measured to reach GLA and GHA levels (there is no obvious corrosion visible to the naked eye on the surface of the glaze layer).

[0062] Example 2

[0063] The specific preparation steps of a blush physical coloring architectural ceramic are as follows: 1: Prepare a ceramic tile blank by dry pressing ceramic body powder, and perform a drying treatment. Then, apply a base glaze on the surface of the dried blank by spraying and perform a drying treatment. The chemical composition of the base glaze includes: by mass percentage, SiO 2 54.5%; Al 2 O 3 29.1%; Fe 2 O 3 0.4%; TiO 2 0.1%; CaO 0.7%; MgO 0.2%; K 2 O 2.4%; Na 2 O 3.4%; ZrO 2 5.8%; loss on ignition 3.4%. The specific gravity of the base glaze is controlled to be 1.40 g / cm 3 , and the glazing amount is 500 g / m 2 .

[0064] 2: Weigh 60 parts by mass of a calcium-zinc-based low-temperature frit (by mass percentage, its chemical composition is: SiO 2 59.3%; Al 2 O 3 8.7%; CaO 13.2%; MgO 1.9%; K 2 O 6%; Na 2 O 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, 0.3 parts by mass of sodium polyacrylate, and place them together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water in a ball mill tank, and perform a grinding treatment using a ball mill; then, control the sieve residue of the glaze slurry to be 0.3 - 0.5 wt% (325 mesh) by the ball milling time, and control the specific gravity of the glaze slurry to be 1.60 g / cm 3 by the water content, and thus the effect glaze can be prepared for standby. The chemical composition of the effect glaze includes: by mass percentage, SiO 2 41.94%; Al 2 O 3 8.72%; Fe 2 O 3 0.08%; TiO 2 9.97%; CaO 7.93%; MgO 1.16%; K 2 O 3.93%; Na 2 O 0.83%; BaO 0.97%; ZnO 20.70%; ZrO 2 2.69%; loss on ignition 1.08%.

[0065] 3: Apply the effect glaze on the surface of the dried ceramic tile blank with underglaze by the method of dipping glazing, and the glazing amount is 900 g / m 2 , and then carry out the drying treatment.

[0066] 4: Use a roller hearth kiln to fire the dried tile blank with the effect glaze applied, the firing temperature is 1160 °C, and the firing time is 60 min.

[0067] 5: After the firing is completed, carry out edge grinding, film pasting, and packing treatments to obtain the physical coloration building ceramics with a blush effect.

[0068] Measure the chromaticity values of the glaze surface of the physical coloration building ceramics with a blush effect by using a full-automatic color difference meter as: L* = 82.6, a* = 3.1, b* = -1.9. The chromaticity red value of the ceramic glaze is greater than the blue value, showing a light purplish red overall, and at the same time having a unique "cloud-dipping seedling" blush aesthetic effect. According to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of chemical resistance), the acid resistance of the prepared physical coloration building ceramics with a blush effect can reach grades GLA and GHA.

[0069] Example 3

[0070] The specific preparation steps of a physical coloration building ceramics with a blush effect are as follows: 1: Prepare a ceramic tile blank by dry pressing the ceramic body powder and carry out the drying treatment. Then, apply the underglaze on the surface of the dried tile blank by the spraying glazing method and carry out the drying treatment. The chemical composition of the underglaze includes: by mass percentage, SiO 2 54.5%; Al 2 O 3 29.1%; Fe 2 O 3 0.4%; TiO 2 0.1%; CaO 0.7%; MgO 0.2%; K 2 O 2.4%; Na 2 O 3.4%; ZrO 2 5.8%; loss on ignition 3.4%. The specific gravity of the underglaze is controlled to be 1.45 g / cm 3 , and the glazing amount is 650 g / m 2 .

[0071] 2: Weigh 45 parts by mass of a calcium-zinc-based low-temperature frit (by mass percentage, its chemical composition is: SiO 2 59.3%; Al 2 O 3 8.7%; CaO 13.2%; MgO 1.9%; K 2 O 6%; Na 2O 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, and 0.1 part by mass of sodium tripolyphosphate, 0.3 part by mass of sodium citrate, and placed in a ball mill tank 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 residue on sieve of the glaze slip is controlled to be 0.3 - 0.5 wt% (325 mesh) by the ball milling time, and the specific gravity of the glaze slip is controlled to be 1.70 g / cm 3 , and thus the effect glaze can be prepared for later use. The chemical composition of the effect glaze includes: by mass percentage, SiO 2 30.83%; Al 2 O 3 5.73%; Fe 2 O 3 0.04%; TiO 2 14.96%; CaO 5.95%; MgO 0.86%; K 2 O 2.87%; Na 2 O 0.62%; BaO 0.73%; ZnO 33.51%; ZrO 2 3.36%; loss on ignition 0.54%.

[0072] 3: Apply the effect glaze on the surface of the dried ceramic tile blank with the bottom glaze by the method of pouring glaze, and the glaze application amount is 700 g / m 2 , and then carry out the drying treatment.

[0073] 4: Fire the dried tile blank with the effect glaze applied using a roller hearth kiln, the firing temperature is 1130 °C, and the firing time is 35 min.

[0074] 5: After firing is completed, carry out edge grinding, film pasting, and packing treatments, and thus the physical coloring building ceramic with a red halo can be obtained.

[0075] The chromaticity values of the glaze surface of the physical coloring building ceramic with a red halo measured using a full - automatic color difference meter are: L* = 69.8, a* = 2.1, b* = - 0.9. The chromaticity red value of the ceramic glaze is greater than the blue value, showing a light purplish - red overall, and at the same time having a unique aesthetic effect of "soaking cloud seedlings" with a red halo. According to GB / T 3810.13 - 2016 (Test methods for ceramic tiles - Part 13: Determination of chemical corrosion resistance), the acid - resistant performance of the prepared physical coloring building ceramic with a red halo can reach GLA and GHA levels.

[0076] Example 4

[0077] The specific preparation steps of a physical coloring building ceramic with a red halo are as follows: 1: Prepare a ceramic tile blank by dry pressing ceramic blank powder, and perform a drying treatment. Then, apply a base glaze on the surface of the dried blank by spraying and perform a drying treatment. The chemical composition of the base glaze includes: by mass percentage, SiO 2 54.5%; Al 2 O 3 29.1%; Fe 2 O 3 0.4%; TiO 2 0.1%; CaO 0.7%; MgO 0.2%; K 2 O 2.4%; Na 2 O 3.4%; ZrO 2 5.8%; loss on ignition 3.4%. The specific gravity of the base glaze is controlled to be 1.43 g / cm 3 , and the glaze application amount is 620 g / m 2 .

[0078] 2: Weigh 40 parts by mass of a calcium-zinc-based low-temperature frit (by mass percentage, its chemical composition is: SiO 2 59.3%; Al 2 O 3 8.7%; CaO 13.2%; MgO 1.9%; K 2 O 6%; Na 2 O 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 part 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 tank, and perform a grinding treatment using a ball mill; then, control the screen residue of the glaze slurry to be 0.3 - 0.5 wt% (325 mesh) by the ball milling time, and control the specific gravity of the glaze slurry to be 1.65 g / cm 3 by the water content, and thus the effect glaze can be prepared for standby. The chemical composition of the effect glaze includes: by mass percentage, SiO 2 30.24%; Al 2 O 3 5.23%; Fe 2 O 3 0.04%; TiO 2 17.95%; CaO 5.29%; MgO 0.77%; K 2 O 2.57%; Na 2 O 0.55%; BaO 0.65%; ZnO 28.12%; ZrO 2 8.06%; loss on ignition 0.53%.

[0079] 3: Apply the effect glaze on the surface of the dried ceramic tile blank after applying the base glaze by spraying method, and the glaze application amount is 750 g / m 2 , and then carry out the drying treatment.

[0080] 4: Use a roller hearth kiln to fire the dried tile blank applied with the effect glaze, the firing temperature is 1140 °C, and the firing time is 50 min.

[0081] 5: After the firing is completed, carry out edge grinding, film pasting, and packing treatments to obtain the physical coloring building ceramics with red halo.

[0082] The chromaticity values of the glaze surface of the physical coloring building ceramics with red halo measured by a full-automatic color difference meter are: L* = 69.8, a* = 4.3, b* = -1.6. The chromaticity red value of the ceramic glaze is greater than the blue value, showing a light purplish red as a whole, and at the same time having a unique "soaking cloud seedling" red halo aesthetic effect. According to GB / T 3810.13-2016 (Test methods for ceramic tiles - Part 13: Determination of chemical resistance), the acid resistance of the obtained physical coloring building ceramics with red halo can reach GLA and GHA levels.

[0083] Comparative Example 1 The technical solution of Comparative Example 1 is basically the same as that of Example 2, and the main difference is that: the glaze application amount of the effect glaze in Comparative Example 1 is greater than that in Example 2. In Comparative Example 1, the specific gravity of the effect glaze is controlled to be 1.60 g / cm 3 , and apply the effect glaze on the surface of the dried ceramic tile blank after applying the base glaze by pouring glaze method, and the glaze application amount is 1000 g / m 2 .

[0084] Take the glaze surface photo of the obtained building ceramics by an optical camera, as Figure 6 shown. The chromaticity values of the glaze surface of the physical coloring building ceramics with red halo measured by a full-automatic color difference meter are: L* = 85.6, a* = 1.3, b* = 4.1. The glaze layer shows opacification and loss of transparency, the chromaticity yellow value of the ceramic glaze is greater than the blue value, showing milky white (yellowish) as a whole, and there is no obvious decorative effect.

[0085] Comparative Example 2 The technical solution of Comparative Example 2 is basically the same as that of Example 2, and the main difference is that: the glaze application amount of the effect glaze in Comparative Example 2 is less than that in Example 2. In Comparative Example 2, the specific gravity of the effect glaze is controlled to be 1.60 g / cm 3 , and apply the effect glaze on the surface of the dried ceramic tile blank after applying the base glaze by pouring glaze method, and the glaze application amount is 500 g / m 2 .

[0086] Take the glaze surface photo of the obtained building ceramics by an optical camera, as Figure 7As shown. The chromaticity values of the physical coloring of the matte building ceramic glaze measured by a full-automatic color difference meter are: L* = 71.0, a* = 2.0, b* = -3.4. The glaze layer is in a matte state, the ceramic glaze has a light blue color, and the overall color is relatively single.

[0087] Comparative Example 3 The technical solution of Comparative Example 3 is basically the same as that of Example 1, and the main difference is that: in Comparative Example 3, the TiO 2 , ZrO 2 content in the effect glaze is lower than that in Example 1. In Comparative Example 3, 60 parts by mass of a calcium-zinc-based 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, and 0.15 parts by mass of sodium tripolyphosphate and 0.15 parts by mass of sodium carboxymethylcellulose need to be weighed separately, and placed in a ball mill tank 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 sieve residue of the glaze slurry is controlled to be 0.3 - 0.5 wt% (325 mesh) by the ball milling time, and the specific gravity of the glaze slurry is controlled to be 1.60 g / cm 3 , and thus the effect glaze can be prepared for standby. The chemical composition of the effect glaze includes: by mass percentage, SiO 2 41.28%; Al 2 O 3 8.72%; Fe 2 O 3 0.08%; TiO 2 4.99%; CaO 7.93%; MgO 1.16%; K 2 O 3.93%; Na 2 O 0.83%; BaO 0.97%; ZnO 27.69%; ZrO 2 1.34%; loss on ignition 1.08%.

[0088] The glaze surface photo of the prepared building ceramic is taken by an optical camera, as Figure 8 shown. Local crystallization occurs on the ceramic glaze surface, and white zinc silicate crystal flowers precipitate in the transparent glaze layer, without the physical coloring effect of red halo; and according to GB / T 3810.13 - 2016 (Test methods for ceramic tiles - Part 13: Determination of chemical resistance), the acid resistance of the prepared building ceramic can reach GLC and GHB levels (visible corrosion damage exists at the white crystal flower area).

[0089] Comparative Example 4 The technical solution of Comparative Example 4 is basically the same as that of Example 1, and the main difference is that: in Comparative Example 4, the TiO 2 , ZrO 2The content is higher than that in Example 1. In Comparative Example 4, 40 parts by mass of a calcium-zinc-based 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 carboxymethylcellulose were weighed respectively, and placed in a ball mill tank together with 200 parts by mass of corundum grinding balls and 50 parts by mass of water, and grinding treatment was carried out using a ball mill; then, the sieve residue of the glaze slurry was controlled to be 0.3-0.5 wt% (325 mesh) by the ball milling time, and the specific gravity of the glaze slurry was controlled to be 1.60 g / cm 3 , and thus the effect glaze can be prepared for standby. The chemical composition of the effect glaze includes: by mass percentage, SiO 2 30.90%; Al 2 O 3 5.23%; Fe 2 O 3 0.04%; TiO 2 22.93%; CaO 5.29%; MgO 0.77%; K 2 O 2.57%; Na 2 O 0.55%; BaO 0.65%; ZnO 21.13%; ZrO 2 9.41%; loss on ignition 0.53%.

[0090] The glaze surface photo of the prepared architectural ceramics was taken by an optical camera, as shown in Figure 9 . The glaze surface of the ceramics is crystallized as a whole, and the crystalline phase accumulates in the glaze layer to form white spots, without the physical coloring effect of red halo.

Claims

1. A method for preparing blushing 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 blank 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 mineral composition of the effect glaze includes: by weight, 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 weight 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%; 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, characterized in that 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%, MgO0.1-0.5%, K2O 2-6%, Na2O 2-3.5%, ZrO2 4-8%, and loss on ignition 2-5%.

3. The preparation method according to claim 1, characterized in that 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 glaze or spraying glaze.

4. The preparation method according to claim 1, characterized in that 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%.

5. The preparation method according to claim 1, characterized in that 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 glaze or spraying glaze.

6. The preparation method according to claim 1, characterized in that The firing temperature is 1130~1160℃, and the firing time is 35~60 min.

7. 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.

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

9. The preparation method according to claim 7, characterized in that: After firing, the crystallization phase on the surface of the effect glaze is mainly rutile crystal phase, and rutile has obvious preferred orientation, and the preferred orientation crystal plane is 110.

10. The preparation method according to claim 9, characterized in that: The coupled superposition effect 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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