Color-permeable colorful ceramic and preparation process thereof

Abstract

The invention discloses a color-permeable colorful ceramic and a preparation process thereof, and belongs to the technical field of ceramic preparation processes, a transparent AlON ceramic body is formed by low-temperature diffusion bonding sintering, an adjustable structural color of 480-630 nm is realized through TiO2 / ZrO2 nanocrystalline spacing (180-220 nm), a Sm2O3 chemical color is superposed, delta E is less than or equal to 0.5, and the color is changed along with the angle and does not fade; after decoration firing of a finished product, embossment line patterns can be engraved inside and outside the ceramic body through femtosecond laser, due to the fact that the main body of the ceramic body is high in light transmittance, when light directly irradiates or enters the interior from the top as a bottle, halo of the embossment line patterns engraved inside and outside can be scattered on the surface, and the overall optical effect is improved; the ceramic is suitable for high-grade decorative ceramics such as bottles and ornaments.

Description

TECHNICAL FIELD

[0001] The application discloses a ceramic preparation process technology, in particular to a kind of transparent multicolor ceramic and preparation process thereof. BACKGROUND

[0002] Ceramics is a typical representative of Chinese traditional culture and an important carrier of human history, and is a kind of material indispensable in human production and life, with its extensive use, vivid artistic expression and profound cultural influence on human life, among which, decorative ceramics as an important type of ceramic products, plays an important role in home decoration, art exhibition.

[0003] The existing high-transparency ceramic is sintered at high temperature (>1900 DEG C), which has high energy consumption and long cycle, and the surface coloring only uses chemical pigment spraying process, which is easy to fade, has poor curing effect and insufficient color performance. SUMMARY

[0004] The application aims to solve the above problems and provide a kind of transparent multicolor ceramic and preparation process thereof.

[0005] To achieve the above object, the application provides the following technical scheme: a preparation process of a transparent multicolor ceramic, comprising the following steps:

[0006] (1) mixing AlON powder, sintering aid and refractive index regulator according to weight parts to obtain a matrix ingredient;

[0007] (2) vacuum slip casting the matrix ingredient to obtain a thin-walled green body;

[0008] (3) degreasing the green body;

[0009] (4) diffusion bonding the green body in a vacuum hot-pressing furnace at 850 DEG C and a pressure of 3 MPa, using La2O3-Nb2O3-B2O3-SiO2-Al2O3 glass as an intermediate layer to form a transparent AlON ceramic body;

[0010] (5) finishing and polishing the transparent AlON ceramic body;

[0011] (6) applying a structural color glaze layer on the surface of the polished ceramic body, the structural color glaze layer comprising TiO2 / ZrO2 crystallization component and Sm2O3 coloring component;

[0012] (7) baking the structural color glaze layer at 760 DEG C-800 DEG C for 5-15 min to solidify the structural color glaze layer and form optical matching with the matrix to obtain the transparent multicolor ceramic.

[0013] As a preferred, the matrix ingredient components are as follows in mass fraction:

[0014] 80-90 parts of AlON powder, 5-10 parts of Y2O3, 3-7 parts of Al2O3, 1-3 parts of La2O3.

[0015] As preferred, the components of the intermediate layer are in a molar ratio of:

[0016] 35% of La2O3, 10% of Nb2O5, 40% of B2O3, 10% of SiO2, 5% of Al2O3.

[0017] As preferred, in step (4), the diffusion connection is carried out in an inert atmosphere or vacuum, and the holding time is 20-40 min.

[0018] As preferred, the structural color glaze layer has a thickness of 0.15-0.35 mm and contains 5-10 wt% of TiO2, 3-7 wt% of ZrO2 and 1-3 wt% of Sm2O3.

[0019] As preferred, in step (2), the slurry for vacuum injection has a solid content of 50-60 wt%, a vacuum degree of ≤-0.08 MPa, and an injection time of 15-30 s.

[0020] As preferred, in step (3), the low-temperature glue removal is carried out by increasing the temperature to 580-620 ℃ at a rate of 0.5-2 ℃ / min and holding for 30-60 min.

[0021] As preferred, in step (5), the polished substrate has a wall thickness of 2.0-3.0 mm and a linear light transmittance of ≥80%.

[0022] A kind of color ceramic, is prepared using preparation process, and after product baking, can be engraved in the inside and outside of ceramic body by femtosecond laser.

[0023] Compared with the prior art, the beneficial effects of the present application are:

[0024] The present application adopts low-temperature diffusion connection sintering to form a transparent AlON ceramic body, then realizes 480-630 nm adjustable structural color through TiO2 / ZrO2 nanocrystal spacing (180-220 nm), superimposes Sm2O3 chemical color, ΔE≤0.5, realizes goniochromism and does not fade; after product baking, can be engraved in the inside and outside of ceramic body by femtosecond laser, since the high light transmittance of ceramic body, when light is directly irradiated or as a bottle from the top into the inside, will be scattered on the surface to present the halo of engraved relief pattern inside and outside, improve the overall optical effect, suitable for high-grade decorative ceramics such as bottles and ornaments. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is the chart of orthogonal experiment (mass parts) and result of base formula;

[0026] Figure 2 Orthogonal experiment (mass %) for the structural color glaze layer formula and the chart of the results;

[0027] Figure 3 SEM image of the glass powder after preliminary sintering at 10 µm;

[0028] Figure 4 Microstructure of the glass phase enriched area between the granular crystalline phases on the surface of the structural color glaze layer. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It should be understood that, in the description of the present application, the terms "upper", "lower", "front", "back", "left", "right", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, and are merely used for the purpose of facilitating the description of the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0030] A preparation process of a transparent multi-color ceramic, comprising the following steps:

[0031] (1) A base material mixture of 90 parts of AlON powder, 8 parts of Y2O3, 5 parts of Al2O3, and 2 parts of La2O3 is added to an alumina ball mill tank, with anhydrous ethanol as the medium, a ball-to-material ratio of 2:1, and ball milling at 500 r / min for 24 h to obtain a uniform slurry with D50=0.8 µm. The slurry is dried in a vacuum oven at 60°C for 12 h, and then sieved through a 60-mesh sieve to obtain a flowable powder with a loose bulk density of 0.95 g / cm³;

[0032] (2) A slurry is prepared according to the following proportions: 55 wt% flowable powder, 35 wt% deionized water, 8 wt% acrylic emulsion, and 2 wt% dispersant, with a specific gravity of 1.9 g / cm³ and a viscosity of 800 mPa·s. The slurry is injected into a gypsum mold using vacuum injection, with a slurry solid content of 50-60 wt%, a vacuum degree of ≤-0.08 MPa, and an injection time of 15-30 s. A thin-walled green body with a wall thickness of 2.5 mm is obtained by final dehydration molding and demolding;

[0033] (3) The thin-walled green body is dried in a microwave at 80°C for 30 min, and then is subjected to a low-temperature glue removal treatment by a low-temperature glue removal furnace, the low-temperature glue removal is heated to 600°C at a rate of 2°C / min and is kept for 60 min, and a base ceramic preliminary blank is obtained;

[0034] (4) 35% of La2O3, 10% of Nb2O5, 40% of B2O3, 10% of SiO2 and 5% of Al2O3 are weighed according to the molar ratio, mixed in a corundum crucible, dried in an oven at 160°C for 2 h, and then transferred into a box-type resistance furnace after the adsorbed water is removed, and is heated to 1000°C at a rate of 10°C / min and is kept for 30 min, so that the powder is fully melted, and then is continuously heated to 1450°C at the same rate, and is kept for 45 min until a clear and bubble-free glass liquid is obtained, the glass liquid is transferred into ionized water for quenching, and glass fragments are obtained, the glass fragments are dried in an oven, and then are subjected to ball milling in a planetary ball mill with ethanol as a ball milling medium at a ball milling rate of 500 rpm for 4 h, and a glass powder with a D90 of 10 µm is obtained;

[0035] 70 wt% of the glass powder, 5 wt% of ethyl cellulose and 25 wt% of terpineol are configured into an intermediate layer slurry according to the mass percentage, and after three-roll milling with a viscosity of 25 Pa·s at 23°C for at least 3 cycles, the intermediate layer slurry is coated onto the base ceramic preliminary blank by a curved soft net, the soft net is 325 mesh, the angle of the doctor blade is 75°, the speed is 100 mm / s, and the printing is performed for 2 times, and the wet film thickness is 120 µm, the base ceramic preliminary blank after the coating treatment is transferred into a mesh belt furnace for low-temperature degreasing at 500°C for 30 min, and the organic carrier in the intermediate layer slurry is removed, as shown in Figure 3 the SEM image of the glass powder after the preliminary sintering at 10 µm, a porous skeleton is formed after the preliminary sintering, which prevents the interlayer cavities caused by organic volatilization during the subsequent diffusion connection, the glass powder after the degreasing is in a honeycomb-shaped porous skeleton with a pore size of 1-3 µm, which is beneficial to the subsequent melting flow and wetting, and then the base ceramic preliminary blank after the low-temperature degreasing is transferred into a vacuum hot-pressing furnace, is heated to 850°C at a rate of 5°C / min from 25°C and is kept for 30 min in a N2 atmosphere with a pressure of 0.1 MPa, the furnace pressure is increased to 3 MPa at a rate of 1 MPa / min in a segmented manner, the intermediate layer slurry is leveled and wetted on the surface of the base ceramic preliminary blank at a high temperature to realize the diffusion connection, and a transparent AlON ceramic body is finally formed;

[0036] (5) The transparent AlON ceramic body is polished and finished, the base wall thickness after the polishing is 2.0-3.0 mm, and the linear light transmittance is ≥80%;

[0037] (6) The structural color glaze layer includes TiO2 / ZrO2 crystallization components and Sm2O3 coloring components, and the structural color glaze is formed on the surface of the polished ceramic body by digital inkjet spraying, and the structural color glaze ink is prepared as follows:

[0038] Bi2O3-SiO2 glass chips were obtained by mixing 35% Bi2O3 and 20% SiO2 by mole fraction, heating in a furnace at 1450°C for 45 min, and then water quenching. The Bi2O3-SiO2 glass chips were ball milled for 4 h to obtain a D50 = 1.5 µm batch powder. The batch powder was mixed with D50 = 50 nm TiO2, ZrO2, and Sm2O3 powders in the following mass percentages: 83% batch powder, 7% TiO2, 5% ZrO2, and 2% Sm2O3.

[0039] After mixing, 0.4% dispersant BYK-111 and 2.6% dipropylene glycol methyl ether solvent were added. After three passes of three-roll milling, a structural color glaze ink with a viscosity of 25 ± 2 mPa·s at 23°C was obtained. The TiO2 / ZrO2 ratio was adjusted to achieve an intercrystalline spacing of 180-220 nm after crystallization, satisfying Bragg scattering of 480-630 nm. The Sm2O3 concentration was controlled to achieve a chemical color saturation, ΔE ≤ 0.5. The structural color glaze ink was filtered through a 0.45 µm nylon filter and degassed in a vacuum degassing machine for 15 min before being loaded into a light-proof ink cartridge and stored at 4°C. Before digital inkjet application, the polished ceramic body was preheated in an oven at 80°C to remove surface moisture. Then, a digital inkjet printer was used for laser scanning inkjet printing at a resolution of 600 dpi, with an ink droplet volume of 3.5-5.0 pl and an ink layer thickness of 0.18 ± 0.02 mm. After inkjet printing, UV pre-curing was performed using a 365 nm UV light, with a curing time of 3 s per layer. After application, the sample was fired at 780°C. Since the Bi2O3-SiO2 acts as a low-temperature melting carrier with a softening point of 720 ± 10°C, which is lower than the AlON diffusion bonding temperature of 850°C, the structural color glaze layer can be completely melted and flattened at 780-800°C, avoiding secondary high-temperature damage to the ceramic body. Additionally, the Bi2O3-SiO2 has the effects of refractive index matching and optical enhancement, forming high-low refractive index alternating layers with TiO2 rutile (n ≈ 2.7), enhancing Bragg scattering, and increasing the structural color saturation by 15-20%. B2O3 reduces the melt viscosity, promoting the spreading of the structural color glaze layer on the AlON surface. After melting, the Si-O-Bi network forms a chemical bond with the Al-O bond on the AlON surface, improving the adhesion of the glaze layer.

[0040] As Figure 4The microstructure in the glass phase rich region between the granular crystalline phase on the surface of the structural color glaze layer is shown, the glass phase has a typical phase separation structure, and the phase separation is approximately isolated spherical droplets; the phase separation droplets are uniformly distributed and have a certain short-range order, meeting the conditions of amorphous photon scattering, which forms a special structural color on the macroscopic level, and the Bragg scattering can form a structural color in the range of light blue to red. Under the superimposed coupling of TiO2 / ZrO2 crystallization coloring, the glaze surface can present a deep red halo.

[0041] The following is the corresponding relationship between the verification formula and the optical performance, according to the scheme design orthogonal experiment 16 groups (4x4), test index: transmittance (T%), structural color main wavelength (λ / nm), surface contact angle (θ / °). All samples use the same process (diffusion connection 850℃-30min-3MPa, baking 780℃-10min), only the listed variables are changed. The transmittance is tested by UV-Vis 1000nm, the structural color main wavelength is tested by a spectrophotometer, and the surface contact angle is tested by a water contact angle instrument, as shown in Figure 1 and Figure 2 The orthogonal experiment (mass parts) of the base formula and the results and the orthogonal experiment (mass%) of the structural color glaze layer formula and the results are shown, from which it can be seen that the best base formula: AlON is 88-90 parts, Y2O3 is 7-8 parts, Al2O3 is 5 parts, La2O3 is 2 parts (serial numbers 9-12), the transmittance is 86-88%, the best structural color glaze formula: TiO2 is 7-8%, ZrO2 is 5%, Sm2O3 is 2-2.5% (serial numbers C-D), the main wavelength is 540-555nm, ΔE≤0.6, the comprehensive best scheme: the base formula is 90-8-5-2 parts + the structural color glaze layer is C formula, the final product transmittance is 88%, the main wavelength is 550nm, and the contact angle is 159°;

[0042] After the finished product is baked, the femtosecond laser can be used to carve the relief pattern inside and outside the ceramic body. Since the main body of the ceramic has high transmittance, when the light is directly irradiated or as a bottle or a vessel is irradiated from the top, the light will be scattered on the surface to present the halo of the internal and external carved relief pattern, thereby improving the overall optical effect.

[0043] It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be regarded as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application. Any reference signs in the claims should not be regarded as limiting the claims involved.

[0044] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes only one independent technical solution, and the specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A process for preparing translucent colorful ceramics, characterized in that: The following steps are involved: (1) AlON powder, a sintering aid, and a refractive index modifier are mixed in parts by weight to obtain a matrix batch, wherein the matrix batch components are as follows: 80-90 parts of AlON powder, 5-10 parts of Y2O3, 3-7 parts of Al2O3, and 1-3 parts of La2O3; (2) forming the matrix ingredients by vacuum casting to obtain a thin-walled green body; (3) Debinding the green body; (4) In a vacuum hot pressing furnace at 850°C and 3 MPa, the green body was diffusion bonded using La2O3-Nb2O3-B2O3-SiO2-Al2O3 glass as an intermediate layer to form a transparent AlON ceramic body. The composition of the intermediate layer is 35% La2O3, 10% Nb2O5, 40% B2O3, 10% SiO2, and 5% Al2O3 in a molar ratio. (5) finishing and polishing the transparent AlON ceramic body; (6) applying a structural color glaze layer on the surface of the polished ceramic body, wherein the structural color glaze layer includes a TiO2 / ZrO2 crystallization component and a Sm2O3 coloring component; (7) Baking at 760-800°C for 5-15 minutes to solidify the structural color glaze layer and form an optical match with the substrate to produce translucent colorful ceramics.

2. The process according to claim 1, characterized in that In step (4), diffusion bonding is carried out in an inert atmosphere or in a vacuum, and the holding time is 20-40 minutes.

3. The preparation process of the translucent colorful ceramic according to claim 1, characterized in that: The thickness of the structural color glaze layer is 0.15-0.35 mm, and includes 7 wt % TiO2, 5 wt % ZrO2 and 2 wt % Sm2O3.

4. The process for preparing the translucent colorful ceramic according to claim 1, characterized in that: In step (2), the solid content of the slurry for vacuum grouting is 50-60wt%, the vacuum degree is ≤-0.08MPa, and the grouting time is 15-30s.

5. The process for preparing the translucent colorful ceramic according to claim 1, characterized in that: In step (3), the low-temperature binder removal is heated to 580-620°C at a rate of 0.5-2°C / min and kept at this temperature for 30-60 min.

6. The process for preparing the translucent colorful ceramic according to claim 1, characterized in that: In step (5), the wall thickness of the substrate after polishing is 2.0-3.0 mm, and the linear transmittance is ≥80%.

7. A translucent colorful ceramic, characterized in that: The ceramic body is prepared by the preparation process according to any one of claims 1 to 6, and after the finished product is baked, a femtosecond laser can be used to engrave relief patterns inside and outside the ceramic body.

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