A ceramic trademark glaze and its preparation method

Abstract

This application discloses a ceramic trademark glaze and its preparation method. The trademark glaze comprises 50-60% low-temperature frit; 5-10% zinc oxide; 20-25% zirconium silicate; 8-12% calcined kaolin; 1-2% sodium carboxymethyl cellulose; 0.5-1.0% sodium tripolyphosphate; and 1-5% pigment. The trademark glaze exhibits excellent printing performance, good thixotropic properties, smooth screen printing, and clear line printing without breaks or ink bleeding; it can print clear lines as narrow as 0.3mm. The firing effect is ideal, with pure and vibrant colors and high contrast with the white base glaze; the glaze surface is smooth and even, with no edge curling. It has strong environmental resistance, high hardness after firing, and is resistant to acids and alkalis, maintaining clarity even in harsh outdoor environments for extended periods. The process is widely adaptable, suitable for application to green or unglazed ceramic bodies, and has good compatibility with conventional electrical porcelain firing processes.

Description

Technical Field

[0001] This application belongs to the field of glaze technology, and in particular relates to a ceramic trademark glaze and its preparation method. Background Technology

[0002] As a critical insulating component of power transmission lines, porcelain insulators typically require permanent markings on their surfaces, such as trademarks, specifications, and production traceability codes, for product identification and quality management. Currently, the mainstream technologies for marking in the industry primarily rely on overglaze printing and high-temperature firing processes, specifically including: High-temperature single-fired colored glaze: This process uses metal oxides such as cobalt, chromium, and iron as colorants, mixed with traditional ceramic glazes composed of feldspar, quartz, and clay to form a glaze slurry. This slurry is then applied to the surface of the green or unglazed piece via screen printing, followed by a single firing with the insulator body at a temperature range of 1250℃ to 1380℃. This process is limited by the physicochemical properties of the glaze system itself, resulting in significant shortcomings in its application performance.

[0003] Low-temperature secondary firing glass glaze: This glaze uses lead borosilicate low-melting-point glass as its matrix, with a melting temperature of approximately 800℃ to 950℃. This technology requires a secondary low-temperature firing after the insulator body has been fired at high temperature to fix the markings. However, this secondary firing not only increases energy consumption and cost, but also results in poor thermal expansion coefficient matching and low bonding strength between the low-temperature glaze layer and the ceramic matrix; furthermore, the lead content raises environmental concerns.

[0004] Organic carrier transfer glazing process: This process first uses ink containing organic binders to print the markings, then covers them with a transparent glaze layer and fires them. However, at high temperatures, the vigorous decomposition and volatilization of organic matter can easily form defects such as bubbles and pinholes in the glaze layer, leading to decreased marking clarity and a less dense glaze surface, which may in turn affect the product's insulation performance and long-term reliability.

[0005] In addition, traditional trademark glazes also have the following key defects: The glaze has poor wetting and leveling properties. Existing trademark glaze formulations are not well-matched with the surface energy of pre-treated bisques (with an applied base glaze), resulting in a large contact angle of the glaze on the bisque surface and insufficient wetting. This makes printed patterns prone to problems such as glaze shrinkage, broken lines, jagged edges, or diffusion, severely limiting the precision of the markings. Furthermore, the minimum clear line width required for stable printing is currently typically no less than 0.6 mm, which is insufficient to meet the printing requirements of dense coding in modern electrical porcelain products.

[0006] Poor color stability at high temperatures. During high-temperature firing, complex physicochemical reactions occur between the trademark glaze, the underlying glaze, and the ceramic body, including the interdiffusion of ions. This process can easily alter the chemical environment of the coloring ions, causing uncontrollable hue shifts, reduced brightness, or decreased saturation in the logo color. This makes it difficult to guarantee color consistency between different batches of products, affecting appearance quality and brand recognition.

[0007] Insufficient mechanical strength and durability of the glaze layer. If the glaze layer is too thin, its surface hardness and abrasion resistance are insufficient, making it easily scratched during subsequent production, handling, assembly, and transportation. If the glaze layer is too thick, the increased internal stress can easily cause micro-cracks or lead to the glaze layer peeling off from the substrate. This contradiction between adhesion and abrasion resistance directly affects the durability and readability of the label throughout the product's entire lifecycle.

[0008] The production process suffers from low adaptability and stability. Existing glaze slurries have limited adaptability to the state of the green body, being particularly sensitive to fluctuations in the moisture content of green or unglazed pieces (typically requiring control within a very narrow range of ±0.5%). This poses a significant challenge to controlling the drying process in continuous industrial production. The glaze slurry system exhibits poor suspension stability, easily leading to solid particle sedimentation and liquid phase separation after settling, necessitating frequent stirring. During printing, the glaze slurry tends to dry and form a skin, clogging the screen mesh and resulting in increased printing defects, shortened screen lifespan, and frequent shutdowns for cleaning or screen replacement. This severely reduces production efficiency and continuity, while increasing production costs.

[0009] In view of this, existing methods for manufacturing trademarks on the surface of electrical porcelain insulators have systemic shortcomings in terms of printing precision, color stability, adhesion durability, and process tolerance. Therefore, there is an urgent need to develop a new type of ceramic trademark glaze and its supporting application process to meet the development needs of high-end electrical porcelain products. Summary of the Invention

[0010] This application provides a ceramic trademark glaze and its preparation method to solve the problems existing in related technologies. The technical solution is as follows: In a first aspect, embodiments of this application provide a ceramic trademark glaze, comprising the following components in weight percentage: Low-temperature frit 50-60%; zinc oxide 5-10%; zirconium silicate 20-25%; calcined kaolin 8-12%; sodium carboxymethyl cellulose 1-2%; sodium tripolyphosphate 0.5-1.0%; colorant 1-5%.

[0011] In one embodiment, the following components are included in percentage by mass: Low-temperature frit 49-55%; zinc oxide 6-8%; zirconium silicate 23-25%; calcined kaolin 9-11%; sodium carboxymethyl cellulose 1.2-1.8%; sodium tripolyphosphate 0.6-0.9%; colorant 2-5%.

[0012] In one embodiment, the low-temperature melting block is a PbO-B2O3-SiO2 composite, wherein the contents of PbO, B2O3 and SiO2 are 20-45%, 8-40%, and 10-65%, respectively; and the softening point is 680-720℃.

[0013] In one embodiment, the colorant is any one of cobalt blue, chrome green, praseodymium yellow, or iron black; the iron black is a Fe2O3-MnO2-Cr2O3 composite oxide.

[0014] In one embodiment, the zirconium silicate has a particle size of 0.5-1.0 μm.

[0015] In one embodiment, the alumina content in the calcined kaolin is ≥38%.

[0016] Secondly, embodiments of this application provide a method for preparing ceramic trademark glaze, comprising the following steps: The frit, zinc oxide, zirconium silicate, and kaolin are mixed evenly to obtain a mixed powder; the mixed powder, colorant, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water are placed in a ball mill jar and ball-milled. After ball milling, the specific gravity of the glaze slurry is adjusted to obtain the ceramic trademark glaze.

[0017] In one embodiment, the mass ratio of material:grinding balls:water is 1:(1-2):(0.5-1); the ball milling time is 20-30 hours.

[0018] In one embodiment, the specific gravity of the glaze slurry is adjusted to 1.65-1.70 g / cm³. 3 The application time for cup 4 is 120-180 seconds.

[0019] In one embodiment, the process further includes printing and firing steps: The ceramic trademark glaze is printed and fired on a green body that has been glazed and dried to prepare a ceramic trademark on the ceramic. In one embodiment, printing is done using a 200-300 mesh screen; the firing temperature is 1250-1380℃.

[0020] The advantages or beneficial effects of the above technical solutions include at least the following: The ceramic trademark glaze of this application forms a three-dimensional network structure with CMC and kaolin, giving the glaze ideal thixotropic properties, allowing for the printing of clear lines as small as 0.3 mm wide. Sodium tripolyphosphate prevents glaze flocculation and enhances glaze stability. When the glaze is printed onto the electrical porcelain ligand, the trademark glaze, with low-temperature frit as its main component, melts and fully spreads on the surface of the not-yet-fully vitrified base glaze during the firing stage. Zinc oxide reduces the surface tension of the glaze melt, increases wettability, and promotes spreading, resulting in an "anchored" micro-interlocking structure between the trademark glaze and the body, ensuring a strong and durable bond.

[0021] The above overview is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of this application will become readily apparent from the accompanying drawings and the following detailed description. Attached Figure Description

[0022] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.

[0023] Figure 1 These are diagrams showing the state of the trademark glaze slurry, the body, and after firing in Example 2. Figure 2 The image shows the DSC diagram of the low-temperature fused metal in Example 1. Figure 3 The TG curve of the low-temperature fused metal in Example 1 is shown below. Figure 4 This is an SEM image of the cross-section where the trademark glaze and the base glaze meet in Example 2; Figure 5 This is an XRD pattern of the interface between the trademark glaze and the base glaze in Example 2. Detailed Implementation

[0024] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of this application. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0025] This application provides a ceramic trademark glaze, comprising the following components by weight percentage: Low-temperature frit 50-60%; zinc oxide 5-10%; zirconium silicate 20-25%; calcined kaolin 8-12%; sodium carboxymethyl cellulose 1-2%; sodium tripolyphosphate 0.5-1.0%; colorant 1-5%.

[0026] In one embodiment, the following components are included in percentage by mass: Low-temperature frit 49-55%; zinc oxide 6-8%; zirconium silicate 23-25%; calcined kaolin 9-11%; sodium carboxymethyl cellulose 1.2-1.8%; sodium tripolyphosphate 0.6-0.9%; colorant 2-5%.

[0027] In the ceramic trademark glaze of this application, the low-temperature frit and zinc oxide provide a gradient melting-interface bonding mechanism, enabling the ceramic trademark glaze to "anchor" itself onto the electric porcelain base glaze, ensuring a firm and durable bond. Sodium carboxymethyl cellulose, kaolin, and sodium tripolyphosphate provide a thixotropic-suspension synergistic system; sodium carboxymethyl cellulose and kaolin form a three-dimensional network structure, imparting ideal thixotropic properties to the glaze slurry: high viscosity during standing to prevent sedimentation, and a sharp drop in viscosity during printing and shearing, resulting in smooth screen printing; clear lines without broken lines or ink bleeding; and the ability to print clear lines as small as 0.3 mm wide. Simultaneously, sodium tripolyphosphate can chelate Ca²⁺. + / Mg² + Ions prevent flocculation caused by hard water, ensuring stable glaze without stratification; this provides a foundation for the stability and practicality of the glaze. The fired markings have high hardness (Mohs hardness ≥ 6), are resistant to acid, alkali, and organic solvent wiping, and can remain clear for extended periods in harsh outdoor environments.

[0028] As one embodiment, the low-temperature melting block is a PbO-B2O3-SiO2 composite, wherein the contents of PbO, B2O3 and SiO2 are 20-45%, 8-40%, and 10-65%, respectively; and the softening point is 680-720℃.

[0029] The PbO-B2O3-SiO2 low-temperature frit with a softening point of approximately 680-720℃ is selected. Its maturation temperature is significantly lower than the softening temperature of the electrical porcelain base glaze, which is 1250–1380℃. Therefore, during the firing heating stage (900–1100℃), the trademark glaze melts first and spreads fully on the surface of the base glaze that is not yet fully vitrified, forming an "anchored" micro-interlocking structure with an interlocking depth of 10-15μm. Furthermore, with the further reduction of the surface tension of the glaze melt by zinc oxide, the contact angle can be reduced to <15°, achieving perfect wetting. This promotes the spreading and interlocking of the trademark glaze, resulting in a smooth and even glaze surface without edge curling.

[0030] As one embodiment, the colorant is any one of cobalt blue, chrome green, praseodymium yellow, or iron black; the iron black is a Fe2O3-MnO2-Cr2O3 composite oxide.

[0031] The colored trademark glaze uses cobalt blue (CoAl2O4), praseodymium yellow (Pr:ZrSiO4) spinel-type or zircon-type colorants, rather than simple metal oxides. The colorants do not react with the glaze matrix at high temperatures, and the color centers are encapsulated by inert crystals, resulting in good color stability. Furthermore, with kaolin providing some alumina, the alumina acts as a spinel structure stabilizer, inhibiting the formation of Co in the cobalt blue. 2+ To Co 3+ It maintains the purity of the blue color through oxidation; it inhibits further oxidation of chromium in chromium green (Cr2O3) and further oxidation of elements in iron black (Fe2O3-MnO2-Cr2O3). It provides a highly stable colorant. The marking colors are pure and vibrant (e.g., bright blue, pure green), with high contrast against the white base glaze.

[0032] As one embodiment, the zirconium silicate has a particle size of 0.5-1.0 μm.

[0033] In one implementation method, the alumina content in the calcined kaolin is ≥38%. The alumina in the kaolin forms a three-dimensional network structure with sodium carboxymethyl cellulose, and also acts as a spinel structure stabilizer for colorants.

[0034] This application also provides a method for preparing ceramic trademark glaze, comprising the following steps: The frit, zinc oxide, zirconium silicate, and kaolin are mixed evenly to obtain a mixed powder; the mixed powder, colorant, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water are placed in a ball mill jar and ball-milled. After ball milling, the specific gravity of the glaze slurry is adjusted to obtain the ceramic trademark glaze. In one embodiment, the frit is a PbO-B2O3-SiO2 composite, wherein the contents of PbO, B2O3, and SiO2 are 20-45%, 8-40%, and 10-65%, respectively; and the softening point is 680-720℃.

[0035] In one embodiment, the frit is made from PbO, H3BO3, and quartz powder. Specifically, each raw material is accurately weighed according to the above glass formula; PbO, H3BO3, and quartz powder are placed in a non-metallic container; 3-5% by weight of deionized water or anhydrous ethanol is added and stirred for 20-30 minutes to ensure uniform mixing and form a loose wet powder; the mixture is placed in a corundum crucible (or platinum crucible) and slowly heated from room temperature to 500°C, held for 2 hours; then the temperature is further increased to 1150-1200°C and held for 1.5 hours; the crucible is quickly removed from the furnace; the molten glass is poured into a vigorously stirred flowing cold water bath for rapid cooling and crushing, and the glass slag is repeatedly rinsed with deionized water; it is then placed in a 105±5°C forced-air drying oven and dried for 4-6 hours until constant weight is achieved; the frit is then obtained.

[0036] As one implementation method, the ball milling fineness is controlled to be ≤0.1% residue on a 10,000-mesh sieve.

[0037] In one implementation method, the mass ratio of material: grinding balls: water is 1:(1-2):(0.5-1); the ball milling time is 20-30 hours.

[0038] As one implementation method, the specific gravity of the glaze slurry is adjusted to 1.65-1.70 g / cm³. 3 The coating time for cup 4 is 120-180 seconds. Using the above preparation method, a glaze suitable for printing is obtained.

[0039] One implementation method also includes printing and firing steps: The ceramic trademark glaze is printed and fired on a green body that has been glazed and dried to prepare a ceramic trademark.

[0040] In one implementation method, printing is done using a 200-300 mesh screen; the firing temperature is 1250-1380℃. Printing is performed on the green body after the base glaze has been applied and dried using a 200-300 mesh screen; during firing, the trademark glaze and the base glaze bond together at high temperature, resulting in a strong and durable finish.

[0041] Example 1 Weigh out PbO, boric acid, and quartz powder according to the following proportions: PbO 30%, B2O3 30%, SiO2 40%. Place the PbO, boric acid, and quartz powder in a non-metallic container. Add 4% (by weight) of deionized water and stir for 25 minutes to mix evenly and form a loose wet powder. Load the mixture into an alumina crucible (or platinum crucible) and slowly heat it from room temperature to 500°C, holding it at that temperature for 2 hours. Then continue heating to 1200°C and holding it for 1.5 hours. Quickly remove the crucible from the furnace. Pour the molten glass into a vigorously stirred, flowing cold water bath for rapid cooling and breakage. Rinse the glass slag repeatedly with deionized water. Place it in a 110°C forced-air drying oven and dry for 5 hours until constant weight is achieved. Obtain the aforementioned low-temperature frit, which is a PbO-B2O3-SiO2 composite, for later use.

[0042] Example 2 A mixed powder was prepared by uniformly mixing 55 parts of low-temperature frit, 7 parts of zinc oxide, 23 parts of zirconium silicate, and 10 parts of calcined kaolin. This mixed powder was then combined with 3 parts by weight of cobalt blue, 1.5 parts by weight of CMC, 0.5 parts by weight of STPP, and deionized water in a ball mill jar at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (forehead 4 cup) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency, such as... Figure 1As shown in the left image; printing is performed on a raw ceramic body that has been glazed and dried using a 200-300 mesh screen, as shown. Figure 1 As shown in the middle image, the trademark glaze and the base glaze are fired at 1260℃, and bonded together at high temperature; as shown... Figure 1 As shown in the figure on the right.

[0043] Example 3 A mixed powder was prepared by uniformly mixing 60 parts of low-temperature frit, 5 parts of zinc oxide, 20 parts of zirconium silicate, and 8 parts of calcined kaolin. This mixed powder was then combined with 5 parts by weight of praseodymium yellow, 1 part of CMC, 1 part of STPP, and deionized water in a ball mill jar at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (Ford Cup 4) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency; use a 200-300 mesh screen to print on the green body that has been glazed and dried, and fire at 1260℃, so that the trademark glaze and the base glaze are bonded together at high temperature.

[0044] Example 4 A mixed powder was prepared by uniformly mixing 50 parts of low-temperature frit, 10 parts of zinc oxide, 24 parts of zirconium silicate, and 12 parts of calcined kaolin. This mixed powder was then added to a ball mill jar with 1 part by weight of chrome green, 2 parts of CMC, 1 part of STPP, and deionized water at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (Ford Cup 4) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency; use a 200-300 mesh screen to print on the green body that has been glazed and dried, and fire at 1260℃, so that the trademark glaze and the base glaze are bonded together at high temperature.

[0045] Comparative Example 1 A mixed powder was prepared by uniformly mixing 55 parts of low-temperature frit, 23 parts of zirconium silicate, and 10 parts of calcined kaolin. This mixed powder was then combined with 3 parts by weight of cobalt blue, 1.5 parts by weight of CMC, 0.5 parts by weight of STPP, and deionized water in a ball mill jar at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (Ford Cup 4) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency; use a 200-300 mesh screen to print on the green body that has been glazed and dried, and fire at 1260℃, so that the trademark glaze and the base glaze are bonded together at high temperature.

[0046] Comparative Example 2 A mixed powder was prepared by uniformly mixing 55 parts of low-temperature frit, 7 parts of zinc oxide, 23 parts of zirconium silicate, and 10 parts of calcined kaolin. This mixed powder was then combined with 3 parts by weight of cobalt oxide, 1.5 parts by weight of CMC, 0.5 parts by weight of STPP, and deionized water in a ball mill jar at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (Ford Cup 4) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency; use a 200-300 mesh screen to print on the green body that has been glazed and dried, and fire at 1260℃, so that the trademark glaze and the base glaze are bonded together at high temperature.

[0047] Comparative Example 3 A mixed powder was prepared by uniformly mixing 55 parts of low-temperature frit, 7 parts of zinc oxide, 23 parts of zirconium silicate, and 10 parts of calcined kaolin. This mixed powder was then added to a ball mill jar with 3 parts by weight of cobalt blue, 1.5 parts by weight of CMC, and deionized water at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (Ford Cup 4) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency; use a 200-300 mesh screen to print on the green body that has been glazed and dried, and fire at 1260℃, so that the trademark glaze and the base glaze are bonded together at high temperature.

[0048] Comparative Example 4 A mixed powder was prepared by uniformly mixing 55 parts of low-temperature frit, 7 parts of zinc oxide, and 23 parts of zirconium silicate dry powder. The mixed powder was then added to a ball mill jar with 3 parts by weight of cobalt blue, 1.5 parts of CMC, 0.5 parts of STPP, and deionized water at a material:grinding ball:water mass ratio of 1:1.5:0.7. The mixture was ball-milled for 25 hours, with the fineness controlled to be ≤0.1% residue on a 10,000-mesh sieve. The specific gravity of the glaze slurry was adjusted to 1.65-1.70 g / cm³. 3 Adjust the viscosity (Ford Cup 4) to 120-180 seconds to obtain a glaze paste with a suitable printing consistency; use a 200-300 mesh screen to print on the green body that has been glazed and dried, and fire at 1260℃, so that the trademark glaze and the base glaze are bonded together at high temperature.

[0049] Performance testing: (1) The low-temperature fused PbO-B2O3-SiO2 composite prepared in Example 1 was subjected to DSC / TG testing. The DSC curve is shown in Figure 1. Figure 2 As shown, the TG curve is as follows Figure 3 As shown.

[0050] Thermal testing results show that the PbO-B2O3-SiO2 low-temperature frit begins to soften at 680±15℃ and completely melts at 750℃. Compared to the maturation temperature of 1250-1380℃ for the base glaze, the softening temperature of the low-temperature frit is significantly lower. This results in the trademark glaze melting first and spreading fully on the surface of the not-yet-fully vitrified base glaze during the firing heating stage (900-1100℃), forming an "anchored" micro-interlocking structure; as shown in the SEM image of the cross-section at the joint. Figure 4 ).from Figure 4 It can also be seen that a 15-20μm interdiffusion layer is formed at the interface between the trademark glaze and the base glaze, and the interlocking depth of the interface reaches 10-15μm.

[0051] (2) The coefficient of thermal expansion shall be tested in accordance with GB / T 4339-2022 "Metallic materials thermal expansion test method" or ISO 10549:2017 "Fine ceramics (advanced ceramics, advanced technical ceramics) - Determination of thermal expansion" or ASTM E228 "Standard Test Method for Linear Thermal Expansion of Solid Materials".

[0052] Low-temperature frit PbO-B₂O₃-SiO₂ composite and electrical porcelain base glaze were prepared as Φ5-8 mm × 10-25 mm cylinders or 5 × 5 × 20 mm cuboids. A thermomechanical analyzer (TMA) was used under air or nitrogen atmosphere, with the temperature increased from 25 °C to 800 °C at a rate of 3-5 °C. The change in sample length with temperature was measured. The coefficient of thermal expansion of the low-temperature frit PbO-B₂O₃-SiO₂ composite was calculated to be 8.2 × 10⁻⁶. -6 The coefficient of thermal expansion of the base glaze of the electric porcelain is 7.5-8.0×10⁻⁶℃ (25-800℃). -6 / ℃, which can be well matched.

[0053] (3) The viscosity of the glaze slurries prepared in Example 2 and Comparative Example 4 was measured using a rotational viscometer equipped with a ULA small sample adapter: Brookfield DV3T, at 25±0.5℃; shear rate program: 0.1-100 s. -1 (Rising curve), 100 - 0.1 s -1 (Descending curve); Thixotropic ring test: The test was conducted over a total duration of 5 minutes, and the results are shown in Table 1: Table 1

[0054] Therefore, the glaze paste of this application has a high viscosity when standing, which can prevent sedimentation, while the viscosity drops sharply during printing and shearing, resulting in smooth screen passage. A 250-mesh stainless steel wire mesh with a wire diameter of 34μm was used; at a printing speed of 0.2m / s and a squeegee pressure of 0.3MPa, 100 consecutive prints were performed without any screen clogging.

[0055] (4) The glaze slurry prepared in Example 2 and the glaze slurry prepared in Comparative Example 3 were kept at a constant temperature of 25°C in a 100ml graduated cylinder under vibration-free conditions for 72 hours. The settling height was recorded every 6 hours, and the settling rate was calculated according to the following formula: Settlement rate = (settlement layer height / total height) × 100%; Redispersibility (time required for mixing to restore homogeneity).

[0056] The glaze slurry prepared in Example 2 had a settling rate of 8.5% after 72 hours and a redispersibility time of 15 seconds; while the glaze slurry in Comparative Example 3 had a settling rate of 35.2% after 24 hours, and the bottom clumps could not be completely dispersed. Therefore, the addition of STPP to the trademark glaze of this application can significantly enhance the stability and redispersibility of the glaze slurry.

[0057] (5) The glaze slurries of Examples 2-4 and Comparative Example 1 were applied to the green body after the base glaze was applied and dried, and then fired. The trademark glaze was then observed in real time at 1200℃ using a high-temperature optical contact angle measuring instrument (VAS-1000). The test conditions were N2 protective atmosphere, heating rate of 5℃ / min, and holding time of 30min. The contact angles are shown in Table 2. The surface tension of the glaze melt at 1200℃ was measured using the pendant drop method in a Mo crucible under an Ar protective atmosphere. The results were analyzed using a high-temperature image analysis system and are shown in Table 2.

[0058] Table 2

[0059] The results in Table 2 show that the addition of zinc oxide significantly reduces the contact angle and surface tension, and the changes in contact angle and surface tension are greater with increasing zinc oxide content. Therefore, the trademark glaze melt can spread fully on the surface of the not-yet-fully-vitrified base glaze, achieving better bonding and enhanced adhesion.

[0060] (6) The interdiffusion layer formed at the interface between the trademark glaze and the base glaze was analyzed using XRD. The XRD pattern is shown in the figure. Figure 5 As shown.

[0061] like Figure 5XRD analysis showed that an anorthite-mullite transition phase was formed at the interface between the trademark glaze and the base glaze, significantly enhancing the bonding strength between the two. Shear force testing revealed an interfacial bonding strength of 28.5 ± 3.2 MPa, a 45% improvement over traditional methods. Adhesion testing (cross-cut test) achieved grade 0 (no peeling).

[0062] (7) Using a Konica Minolta CM-2600d spectrophotometer with a D65 light source and a 10° viewing angle, the trademark glazes of Examples 2, 3, and Comparative Example 2 were compared with the reference color before firing. The results are shown in Table 3. The trademark glazes of Examples 2, 3, and Comparative Example 2 were placed outdoors in the same environment for 6 months, and the color change was compared. The results are shown in Table 3. The trademark glazes of Examples 2, 3, and Comparative Example 2 were placed in a 5% hydrochloric acid solution for 24 hours, and the color change was compared. The results are shown in Table 3. Five batches of parallel samples were selected for the above experiments, with three parallel samples in each batch; the average value was taken.

[0063] Table 3

[0064] As can be seen from the data in Table 3, the trademark glaze of this application uses spinel-type or zircon-type pigments to encapsulate the pigments. Compared with simple metal oxides, the pigments do not react with the glaze matrix at high temperatures, and the color centers are encapsulated by inert crystals. The color stability ΔE<1.5 (ΔE<1.5 is the range of color difference that is not visually discernible) is excellent. Even after being placed outdoors for 6 months, the color change remains stable, and it has excellent stability in acidic environments.

[0065] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of those different embodiments or examples.

[0066] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "a plurality of" means two or more, unless otherwise explicitly specified.

[0067] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various variations or substitutions within the technical scope disclosed in this application, and these should all be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A ceramic trademark glaze, characterized in that, Includes the following components, expressed as a percentage by mass: Low-temperature frit 50-60%; zinc oxide 5-10%; zirconium silicate 20-25%; calcined kaolin 8-12%; sodium carboxymethyl cellulose 1-2%; sodium tripolyphosphate 0.5-1.0%; colorant 1-5%.

2. The ceramic trademark glaze according to claim 1, characterized in that, Includes the following components, expressed as a percentage by mass: Low-temperature frit 49-55%; zinc oxide 6-8%; zirconium silicate 23-25%; calcined kaolin 9-11%; sodium carboxymethyl cellulose 1.2-1.8%; sodium tripolyphosphate 0.6-0.9%; colorant 2-5%.

3. The ceramic trademark glaze according to claim 1, characterized in that, The low-temperature frit is a PbO-B2O3-SiO2 composite, wherein the contents of PbO, B2O3 and SiO2 are 20-45%, 8-40% and 10-65%, respectively; and the softening point is 680-720℃.

4. The ceramic trademark glaze according to claim 1, characterized in that, The colorant is any one of cobalt blue, chrome green, praseodymium yellow, or iron black; the iron black is a Fe2O3-MnO2-Cr2O3 composite oxide.

5. A ceramic trademark glaze according to claim 1, characterized in that, The particle size of zirconium silicate is 0.5-1.0 μm; the alumina content in calcined kaolin is ≥38%.

6. A method for preparing a ceramic trademark glaze, characterized in that, Includes the following steps: The frit, zinc oxide, zirconium silicate, and kaolin are mixed evenly to obtain a mixed powder; the mixed powder, colorant, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water are placed in a ball mill jar and ball-milled. After ball milling, the specific gravity of the glaze slurry is adjusted to obtain the ceramic trademark glaze.

7. The method for preparing ceramic trademark glaze according to claim 6, characterized in that, Materials: The mass ratio of grinding balls to water is 1:(1-2):(0.5-1); the grinding time is 20-30 hours.

8. The method for preparing ceramic trademark glaze according to claim 6, characterized in that, Adjust the specific gravity of the glaze slurry to 1.65-1.70 g / cm³. 3 The application time for cup 4 is 120-180 seconds.

9. The method for preparing ceramic trademark glaze according to claim 6, characterized in that, It also includes printing and firing steps: The ceramic trademark glaze is printed and fired on a green body that has been glazed and dried to prepare a ceramic trademark.

10. The method for preparing ceramic trademark glaze according to claim 9, characterized in that, Printing uses 200-300 mesh screen; firing temperature is 1250-1380℃.

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