Colorful ceramic with transparent color and its preparation process

Abstract

The application discloses a kind of transparent multicolor ceramic and its preparation process, belong to ceramic preparation process technical field, including, the application adopts low-temperature diffusion connection sintering forming transparent AlON ceramic body, through TiO2 / ZrO2 Nanocrystalline interval (180-220nm) 480-630nm adjustable structural color is realized, superimposed Sm2O3 chemical color, ΔE≤0.5, realize with angle heterochromia and not fade;After product baking, can be engraved in ceramic body inside and outside by femtosecond laser relief texture pattern, since the high transmittance of ceramic body main body, when light directly irradiates or as bottle ware is shot from top into inside, will be scattered on surface and present the halo of inside and outside engraved relief texture pattern, improve the overall optical effect, applicable to bottle ware and ornament etc. high-grade decorative ceramics.

Description

Technical Field

[0001] This invention discloses a ceramic preparation process, and in particular relates to a translucent multicolor ceramic and its preparation process. Background Technology

[0002] Ceramics are a typical representative of traditional Chinese culture and an important carrier of human development history. They are also an indispensable material in human production and life, influencing human life with their wide range of uses, vivid artistic expression and profound culture. Among them, decorative ceramics, as an important type of ceramic products, play an important role in home decorations and art exhibitions.

[0003] Existing high-transparency ceramics mostly adopt high-temperature (>1900℃) sintering, which is energy-intensive and has a long cycle. Moreover, the surface coloring only adopts chemical pigment spraying process, which is prone to fading and has poor curing effect, resulting in insufficient color performance. Summary of the Invention

[0004] The purpose of this invention is to provide a translucent multicolor ceramic and its preparation process in order to solve the above-mentioned problems.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a preparation process for translucent multicolor ceramics, comprising the following steps:

[0006] (1) Mix AlON powder, sintering aid and refractive index modifier according to the weight parts to obtain matrix ingredients;

[0007] (2) The matrix materials are formed by vacuum injection molding to obtain a thin-walled green body;

[0008] (3) Perform glue removal treatment on the green body;

[0009] (4) In a vacuum hot press furnace at 850°C and 3MPa, a transparent AlON ceramic body is formed by diffusion bonding of the green body with La2O3-Nb2O3-B2O3-SiO2-Al2O3 glass as an intermediate layer.

[0010] (5) Refine and polish the transparent AlON ceramic body;

[0011] (6) Apply a structural color glaze layer to the polished ceramic body surface. The structural color glaze layer includes TiO2 / ZrO2 crystallization components and Sm2O3 coloring components.

[0012] (7) Bake the colored glaze at 760℃-800℃ for 5-15 minutes to solidify the structural color glaze layer and form an optical match with the substrate to obtain translucent multicolor ceramics.

[0013] As a preferred embodiment, the matrix ingredients are as follows by mass parts:

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

[0015] Preferably, the components of the intermediate layer are in the following molar ratio:

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

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

[0018] Preferably, the thickness of the structural glaze layer is 0.15-0.35 mm, and it includes 5-10 wt% TiO2, 3-7 wt% ZrO2 and 1-3 wt% Sm2O3.

[0019] Preferably, in step (2), the solid content of the grout used for vacuum grouting is 50-60wt%, the vacuum degree is ≤-0.08MPa, and the grouting time is 15-30s.

[0020] Preferably, in step (3), the low-temperature debinding is heated to 580-620℃ at a rate of 0.5-2℃ / min and held at that temperature for 30-60min.

[0021] Preferably, in step (5), the thickness of the substrate wall after polishing is 2.0-3.0 mm, and the linear transmittance is ≥80%.

[0022] A translucent multicolor ceramic is prepared using a specific process, and after the finished product is baked, relief patterns can be engraved on the inside and outside of the ceramic body using a femtosecond laser.

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

[0024] This invention employs low-temperature diffusion bonding sintering to form a transparent AlON ceramic body, and then achieves an adjustable structural color of 480-630nm through the TiO2 / ZrO2 nanocrystal spacing (180-220nm), superimposed with Sm2O3 chemical color, ΔE≤0.5, to achieve color variation at different angles and non-fading. After the finished product is baked, femtosecond laser can be used to engrave relief patterns on the inside and outside of the ceramic body. Due to the high light transmittance of the ceramic body, when light shines directly on it or when it shines into the interior from the top of the bottle, it will scatter on the surface to present the halo of the internal and external engraved relief patterns, improving the overall optical effect. It is suitable for high-end decorative ceramics such as bottles and ornaments. Attached Figure Description

[0025] Figure 1 The graph shows the orthogonal experiment (parts by mass) of the matrix formulation and the results.

[0026] Figure 2 Charts showing the orthogonal experiments (mass %) and results of the structural color glaze layer formulation;

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

[0028] Figure 4 This refers to the microstructure within the glass phase enrichment region between the granular crystalline phases on the surface of the structural glaze layer. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. In this description, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] A process for preparing translucent multicolor ceramics includes the following steps:

[0031] A matrix mixture consisting of 90 parts by weight of AlON powder, 8 parts by weight of Y2O3, 5 parts by weight of Al2O3, and 2 parts by weight of La2O3 was added to an alumina ball mill jar. Anhydrous ethanol was used as the medium, and the ball-to-powder ratio was 2:1. The mixture was ball-milled at 500 r / min for 24 h to obtain a uniform slurry with D50 = 0.8 µm. The slurry was dried in a vacuum oven at 60 °C for 12 h and then passed through a 60-mesh sieve to obtain a flowable powder with a loose bulk density of 0.95 g cm⁻³.

[0032] The grouting solution is prepared according to the following ratio: 55wt% fluid powder, 35wt% deionized water, 8wt% acrylic emulsion and 2wt% dispersant, with a specific gravity of 1.9g / cm³ and a viscosity of 800mPa·s. The grouting solution is injected into the plaster mold using vacuum grouting. The solid content of the grout is 50-60wt%, the vacuum degree is ≤-0.08MPa, and the grouting time is 15-30s. Finally, the grouting solution is dehydrated, molded and demolded to obtain a thin-walled green body with a wall thickness of 2.5mm.

[0033] (3) After drying the thin-walled green body under microwave at 80℃ for 30 min, it is debonded in a low-temperature debonding furnace. The low-temperature debonding process involves heating the green body to 600℃ at 2℃ / min and holding it for 60 min to obtain the matrix ceramic green body.

[0034] (4) Weigh 35% La2O3, 10% Nb2O5, 40% B2O3, 10% SiO2, and 5% Al2O3 by molar ratio, mix them in a corundum crucible, and dry them in an oven at 160℃ for 2 hours to remove adsorbed water. Then transfer the powder to a box-type resistance furnace and raise the temperature from 25℃ to 1000℃ at a rate of 10℃ / min and hold for 30 minutes to fully melt the powder. Then continue to raise the temperature to 1450℃ at the same rate and hold for 45 minutes until a clear glass melt without bubbles is obtained. Transfer the glass melt to deionized water for quenching to obtain glass fragments. Dry the glass fragments in an oven and then ball mill them in a planetary ball mill with ethanol as the ball milling medium at a ball milling rate of 500 rpm for 4 hours to obtain glass powder with D90≤10µm.

[0035] A slurry consisting of 70 wt% glass powder, 5 wt% ethyl cellulose, and 25 wt% terpineol was prepared by weight percentage. After at least three cycles of three-roll milling at 23°C with a viscosity of 25 Pa·s, the slurry was coated onto the ceramic substrate using a 325-mesh curved screen. The squeegee angle was 75°, the speed was 100 mm / s, and two coats were applied, resulting in a wet film thickness of 120 µm. The coated ceramic substrate was then transferred to a mesh belt furnace and heated at 500°C for 30 min for low-temperature degreasing to remove the organic carriers from the slurry. Figure 3 The image shown is a SEM image of the glass powder after initial sintering at 10µm. After initial sintering, a porous framework is formed to prevent interlayer voids caused by organic volatilization during subsequent diffusion bonding. After degreasing, the glass powder has a honeycomb porous framework with a pore size of 1-3µm, which is conducive to subsequent melting flow and wetting. Then, the low-temperature degreased matrix ceramic blank is transferred to a vacuum hot press furnace and heated from 25°C to 850°C at 5°C / min in a 0.1MPa N2 atmosphere and held for 30min. The gas pressure in the furnace is increased in stages at a rate of 1MPa / min to 3MPa. The coated intermediate layer slurry flows and wets the surface of the matrix ceramic blank at high temperature to achieve diffusion bonding and finally form a transparent AlON ceramic body.

[0036] (5) The transparent AlON ceramic body is finely finished and polished. After polishing, the thickness of the substrate wall 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. The structural color glaze is formed by digital inkjet coating on the polished ceramic body surface. The structural color glaze ink is prepared as follows:

[0038] 35% Bi2O3 and 20% SiO2 were mixed by molar fraction and heated in a furnace at 1450°C for 45 min to melt them. After water quenching, Bi2O3-SiO2 glass fragments were obtained. The Bi2O3-SiO2 glass fragments were ball-milled for 4 h to obtain a feed powder with D50=1.5µm. The feed powder was then mixed with TiO2, ZrO2, and Sm2O3 powders with D50=50nm according to the following mass percentages: 83% feed 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. The mixture was then milled three times using a three-roll mill to obtain a structural color glaze ink with a viscosity of 25±2 mPa·s at 23°C. The TiO2 / ZrO2 ratio was adjusted to achieve a crystallization intergranular spacing of 180–220 nm, satisfying Bragg scattering at 480–630 nm. The Sm2O3 concentration was used to control the chemical color saturation, with ΔE ≤ 0.5. The structural color glaze ink was filtered through a 0.45µm nylon filter and degassed in a vacuum degassing machine for 15 min before being stored in a light-proof ink cartridge at 4°C. Before digital inkjet coating, the polished ceramic body was preheated in an oven at 80°C to remove surface moisture. Then, laser scanning inkjet printing was performed using a digital inkjet printer at a resolution of 600 dpi, with droplet volume set to 3.5–5.0 p1 and ink layer thickness set to 0.18±0.02 mm. After inkjet printing using an industrial camera and laser ranging, 365nm UV pre-curing is applied, with curing time at 3 seconds per layer. After coating, the material is baked at 780°C. Since Bi2O3-SiO2 serves 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 at 780-800°C, avoiding secondary high-temperature damage to the ceramic body. Furthermore, Bi2O3-SiO2 has the effect of refractive index matching and optical enhancement, forming a high-low refractive index alternating layer 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 chemical bonds with the Al-O bonds on the AlON surface, improving the adhesion of the glaze layer.

[0040] like Figure 4The image shows the microstructure within the glass phase enrichment region between the granular crystalline phases on the surface of the structural color glaze. The glass phase exhibits a typical phase separation structure, with the phases appearing as approximately isolated spherical droplets. These phase droplets are generally uniformly distributed and possess a certain degree of short-range order, satisfying the conditions for amorphous photon scattering. This results in a unique structural color on a macroscopic scale. Utilizing its Bragg scattering, a structural color ranging from pale blue to red can be formed. Under the superimposed coupling effect of TiO2 / ZrO2 crystallization coloring, this can lead to a deep red iridescence on the glaze surface.

[0041] The following is a verification of the correspondence between the formulation and optical performance. Sixteen orthogonal experimental groups (4×4) were designed according to the scheme. The test indicators were: transmittance (T%), dominant wavelength of structural color (λ / nm), and surface contact angle (θ / °). All samples used the same process (diffusion bonding 850℃-30min-3MPa, baking 780℃-10min), only the listed variables were changed. Transmittance was tested using UV-Vis 1000nm, dominant wavelength of structural color was measured using a spectrophotometer, and surface contact angle was measured using a water contact angle meter. Figure 1 and Figure 2 The figures show the orthogonal experiments (parts by mass) and results of the matrix formulation and the orthogonal experiments (%) of the structural color glaze formulation, respectively. It can be seen that the optimal matrix formulation is: 88-90 parts AlON, 7-8 parts Y2O3, 5 parts Al2O3, and 2 parts La2O3 (numbers 9-12), with a transmittance of 86-88%. The optimal structural color glaze formulation is: 7-8% TiO2, 5% ZrO2, and 2-2.5% Sm2O3 (numbers CD), with a dominant wavelength of 540-555nm and ΔE≤0.6. The overall optimal solution is: a matrix formulation of 90-8-5-2 parts + a structural color glaze formulation of C, resulting in a final product with a transmittance of 88%, a dominant wavelength of 550nm, and a contact angle of 159°.

[0042] After the finished product is baked, a femtosecond laser can be used to engrave relief patterns inside and outside the ceramic body. Because the ceramic body has high light transmittance, when light shines directly on it or when it shines into the interior from the top of the bottle, it will scatter on the surface to present the halo of the relief patterns inside and outside, thus improving the overall optical effect.

[0043] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0044] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. 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 can be understood by those skilled in the art.

Claims

1. A preparation process for translucent multicolor ceramics, characterized in that, Includes the following steps: (1) Mix AlON powder, sintering aid and refractive index modifier by weight to obtain matrix material. The matrix material components by weight are: 80-90 parts of AlON powder, 5-10 parts of Y2O3, 3-7 parts of Al2O3 and 1-3 parts of La2O3. (2) The matrix materials are formed by vacuum injection molding to obtain a thin-walled green body; (3) Perform glue removal treatment on the green body; (4) In a vacuum hot press furnace at 850℃ and 3MPa, a transparent AlON ceramic body is formed by diffusion bonding of the green body with La2O3-Nb2O3-B2O3-SiO2-Al2O3 glass as an intermediate layer. The composition of the intermediate layer is as follows according to the molar ratio: 35% La2O3, 10% Nb2O5, 40% B2O3, 10% SiO2, and 5% Al2O3. (5) Refine and polish the transparent AlON ceramic body; (6) Apply a structural color glaze layer to the polished ceramic body surface. The structural color glaze layer includes the common crystallization component of TiO2 and ZrO2 and the coloring component of Sm2O3. (7) Bake the colored glaze at 760℃-800℃ for 5-15 minutes to solidify the structural color glaze layer and form an optical match with the ceramic body to obtain translucent multicolor ceramic.

2. The preparation process of translucent multicolor ceramics according to claim 1, characterized in that, In step (4), diffusion bonding is carried out in an inert atmosphere or vacuum for 20-40 minutes.

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

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

5. The preparation process of translucent multicolor ceramics according to claim 1, characterized in that, In step (3), the glue is discharged and heated to 580-620℃ at a rate of 0.5-2℃ / min and kept at that temperature for 30-60min.

6. The preparation process of translucent multicolor ceramics according to claim 1, characterized in that, In step (5), the ceramic body wall thickness after polishing is 2.0-3.0 mm, and the linear light transmittance is ≥80%.

7. A translucent multicolor ceramic, characterized in that, It is prepared by the preparation process described in any one of claims 1-6, and after the finished product is baked, the relief pattern is engraved on the inside and outside of the ceramic body by femtosecond laser.

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