High-chemical-stability cloud transmutation glaze and preparation method thereof

Abstract

The invention discloses a high-chemical-stability cloud transmutation glaze and a preparation method thereof, and relates to the technical field of ceramic glazes, and the high-chemical-stability cloud transmutation glaze is prepared from the following components: high-boron frit, low-expansion frit, potassium feldspar, quartz, calcite, calcined talc, calcined zinc oxide, china clay A, china clay B, titanium dioxide, a ceramic colorant and vanadium pentoxide. Wherein the china clay A is selected from kaolin containing 0.05-0.4 wt% of rare earth oxide, and the china clay B is selected from large-particle suspended kaolin with 325-mesh screen residue less than or equal to 0.1% and ignition loss of 5-8%. The high-chemical-stability cloud transmutation glaze provided by the invention has a natural and elegant cloud transmutation artistic effect which is far better than that of the traditional double-layer or multi-layer transmutation glaze; the chemical stability is obviously improved, and the chemical stability can pass the most rigorous 200-turn dishwasher cycle test in European ICTS.

Description

Technical Field

[0001] This invention relates to the field of ceramic glaze technology, and in particular to a highly chemically stable cloud-shaped kiln-transformed glaze and its preparation method. Background Technology

[0002] Daily-use ceramics mainly include three categories: fine porcelain, stoneware, and earthenware. Among them, stoneware, due to its relatively low firing temperature (1180~1240℃) and moderate water absorption (0.5%~3%), is particularly suitable for decoration with colored glazes. Kiln-fired stoneware, with its unpredictable artistic effects, is highly favored by the market. Traditional kiln-fired glazes often employ double or multi-layer reactive glaze systems. While highly decorative, these systems typically introduce significant amounts of alkali metal oxides, calcium and magnesium oxides, or barium oxides to achieve phase separation or crystallization effects. In the high-temperature, high-pressure environment of dishwashers containing strong alkaline detergents and surfactants, these components are prone to ion exchange or hydrolysis reactions, leading to defects such as glaze loss of gloss, rainbow interference colors, frosting, or fading.

[0003] Currently, the high-end stoneware market in Europe and America generally implements extremely strict internal control standards for dishwasher resistance testing. The most representative of these standards is the continuous 200 rpm (approximately 600 hours) dishwasher cycle test (using special dishwasher detergent and surfactants, 65~75℃, strong alkaline + enzyme environment).

[0004] In existing technologies, although single-layer glazes are simple to process and low in cost, it is difficult to achieve both the rich cloud-like kiln transformation effect and the high chemical stability required to pass the aforementioned 200 rpm dishwasher test. It is difficult to achieve both at the same time.

[0005] Therefore, there is an urgent need to develop a new type of kiln-transformed glaze that can achieve a cloud-like kiln-transformation artistic effect under single-layer glazing conditions, and whose chemical stability is sufficient to pass the rigorous test of a 200 rpm dishwasher. Summary of the Invention

[0006] To solve the above-mentioned technical problems, the present invention provides a highly chemically stable cloud-shaped kiln-transformed glaze and its preparation method, the specific technical solution of which is as follows: A highly chemically stable cloud-shaped kiln-transformed glaze, by weight, comprises the following components: 20-27 parts high-boron frit, 15-20 parts low-expansion frit, 10-20 parts potassium feldspar, 15-25 parts quartz, 3-6 parts calcined talc, 3-7 parts calcined zinc oxide, 3-7 parts kaolin A, 5-10 parts kaolin B, 4-7 parts titanium dioxide, 0.1-12 parts ceramic colorant, and 1-3 parts vanadium pentoxide. The kaolin A is selected from kaolin containing 0.05-0.4 wt% rare earth oxides, and the kaolin B is selected from large-particle suspended kaolin with a 325-mesh sieve residue ≤0.1% and a loss on ignition of 5%-8%.

[0007] Preferably, by mass percentage: The high-boron frit is composed of the following components: SiO2 42%~48%, Al2O3 6%~10%, B2O3 18%~25%, CaO 0.5%~4%, MgO 0~2%, ZnO 2%~6%, BaO 0~1%, Na2O 3%~7%, K2O 4%~8%, Li2O 0~1.5%, ZrO2 0~2%; The low-expansion frit is made of the following components: SiO2 48%~55%, Al2O3 12%~18%, B2O3 3%~8%, CaO 8%~14%, MgO 3%~7%, ZnO 0~3%, BaO 0~2%, Na2O 1%~4%, K2O 3%~6%, Li2O 1%~3%, ZrO 0~4%.

[0008] Preferably: The raw material composition of the high-boron fused block further includes: 0.8%~2.5% phosphorus source compound and 0.3%~1.2% cerium oxide, wherein the phosphorus source compound is selected from ammonium dihydrogen phosphate or calcium phosphate; The raw material composition of the low expansion melt also includes 1.0% to 3.0% calcium fluoride.

[0009] Preferably, the porcelain clay A is Guizhou kaolin, and the porcelain clay B is Jiepai kaolin.

[0010] The present invention also provides a preparation method for preparing a highly chemically stable cloud-shaped glaze as described in any one of the above claims, the preparation method comprising the following steps: S1. Weigh the glaze components of the high chemical stability cloud kiln-transformed glaze according to the weight parts, mix them, add the dispersion medium and ball milling medium, and then ball mill to obtain the glaze slurry; S2. Apply the glaze slurry to the surface of the porcelain body to obtain a glaze body; S3. Dry the glaze body to a moisture content of ≤1%, and keep it at 100~130℃ for 0.5~2 hours; S4. The glaze body obtained in step S3 is fired in an oxidizing atmosphere. After firing, a highly chemically stable cloud-shaped glaze is obtained and applied to the ceramic surface.

[0011] Preferably, in step S1, the dispersion medium is a mixture of water and a dispersant, the dispersant being selected from polycarboxylate or sodium tripolyphosphate, and the amount added is 0.1% to 0.4% of the total mass of the glaze; the ball milling medium is alumina balls or zirconia balls, wherein the mass ratio of glaze, milling balls, and dispersion medium is 1:(1.8 to 2.2):(0.65 to 0.75), the ball milling time is 18 to 36 hours, and the average particle size of the resulting glaze slurry is 40 to 60 μm.

[0012] Preferably, in step S2, the glazing method is immersion glazing, glazing pouring glazing or glazing spraying glazing, and the glaze layer thickness is 0.25~0.45mm.

[0013] Preferably, in step S4, the firing temperature is 1190~1230℃, and the highest temperature is held for 15~50 minutes. The heating rate is ≤120℃ / h before 1000℃ and ≤80℃ / h after 1000℃.

[0014] Preferably, the high boron frit is prepared by the following steps: after the raw material components of the high boron frit are mixed evenly, it is melted at 1200~1250℃ for 2~3.5 hours, and a weak oxidizing atmosphere is maintained during the melting process. After melting, it is water-quenched into frit particles, dried, and then ball-milled until the residue on a 325-mesh sieve is ≤1.5%.

[0015] Preferably, the low-expansion frit is prepared by the following steps: after the raw materials and components of the low-expansion frit are mixed evenly, it is melted at 1220~1300℃ for 2~3 hours, maintaining an oxidizing atmosphere during the melting process. After melting, it is water-quenched into frit particles, dried, and then ball-milled until the residue on a 325-mesh sieve is ≤1.0%, thus obtaining the frit.

[0016] The high chemical stability cloud-shaped kiln-transformed glaze provided by this invention has the following beneficial effects: The glaze presents a natural, flowing, layered, and silk-textured cloud-like kiln-transformation artistic effect, far surpassing traditional double-layer or multi-layer kiln-transformation glazes. With significantly improved chemical stability, it can pass the most stringent 200 rpm dishwasher cycle test of the European ICTS. The glaze gloss retention rate is high, with no loss of gloss, rainbow interference color, frosting or fading. The pass rate is extremely high, meeting the most stringent internal control standards of the high-end stoneware market in Europe and the United States, and greatly enhancing the export competitiveness of the product. Detailed Implementation

[0017] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below. The description in this part is only exemplary and explanatory, and should not be used to limit the scope of protection of the present invention in any way.

[0018] This embodiment provides a highly chemically stable cloud-shaped kiln-transformed glaze, which, by weight, comprises the following components: 20-27 parts of high-boron frit, 15-20 parts of low-expansion frit, 10-20 parts of potassium feldspar, 15-25 parts of quartz, 3-6 parts of calcite, 3-7 parts of calcined talc, 3-7 parts of calcined zinc oxide, 3-7 parts of kaolin A, 5-10 parts of kaolin B, 4-7 parts of titanium dioxide, 0.1-12 parts of ceramic colorant, and 1-3 parts of vanadium pentoxide. Kaolin A is selected from kaolin containing 0.05-0.4 wt% rare earth oxides, and kaolin B is selected from large-particle suspended kaolin with a 325-mesh sieve residue ≤0.1% and a loss on ignition of 5%-8%.

[0019] Specifically, the high chemical stability cloud-like kiln-transformation glaze provided in this embodiment achieves the dual goals of a single-layer glaze simultaneously possessing rich and natural cloud-like kiln-transformation effects and high chemical stability through the following technical solutions: A high-glass-transformation base glaze is constructed by combining high-boron frit and low-expansion frit. The high-boron frit provides 18%~25% B2O3, making the glass phase ratio in the glaze greater than 85%. This significantly reduces the alkali metal oxides (total Na2O and K2O controlled below 10%) and calcium, magnesium and barium components in traditional kiln-fired glazes that are easily attacked by strong alkalis in dishwashers. This fundamentally blocks ion exchange and hydrolysis channels, achieving extremely high chemical stability.

[0020] By rationally combining potassium feldspar, quartz, calcite, calcined talc, and calcined zinc oxide, the medium-temperature viscosity and high-temperature surface tension of the glaze are further optimized, creating a suitable liquid phase environment for subsequent phase separation.

[0021] Two key types of specially selected kaolin were introduced: Kaolin A (containing 0.05~0.4wt% rare earth oxides) releases trace amounts of Ce at high temperatures. 4+ / Ce 3+ La 3+ The rare earth ions with variable valence exhibit strong redox coupling with vanadium pentoxide, significantly reducing the phase separation activation energy of vanadium. This allows vanadium to form soft, layered vanadium blue-vanadium yellow-vanadium green gradient clouds within the glaze layer. At the same time, the rare earth ions promote local liquid-liquid phase separation of titanium dioxide, forming a hazy, milky base, presenting a sophisticated "cloud kiln transformation" artistic effect.

[0022] Porcelain clay B (325 mesh sieve residue ≤0.1%, loss on ignition 5%~8%) provides microbubble channels generated by the ultrafine particle size and appropriate amount of organic matter loss on ignition, making the local viscosity gradient of the high-temperature glaze melt smoother, allowing the cloud-like texture to be fully stretched and flowing naturally, while ensuring the long-term suspension stability of the glaze slurry and the uniform glaze thickness.

[0023] The synergistic effect of ceramic colorants with the vanadium-titanium-rare earth system further broadens the hue range, making the cloud effects richer and more varied.

[0024] The synergistic effect of the above-mentioned components and their proportions enables this embodiment to achieve the following beneficial effects under single-layer glaze conditions: The glaze presents a natural, flowing, layered, and silk-textured cloud-like kiln-transformation artistic effect, far surpassing traditional double-layer or multi-layer kiln-transformation glazes. With significantly improved chemical stability, it can pass the most stringent 200 rpm dishwasher cycle test of the European ICTS. The glaze gloss retention rate is high, with no loss of gloss, rainbow interference color, frosting or fading. The pass rate is extremely high, meeting the most stringent internal control standards of the high-end stoneware market in Europe and the United States, and greatly enhancing the export competitiveness of the product.

[0025] Furthermore, by mass percentage: The high-boron frit is made from the following components: SiO2 42%~48%, Al2O3 6%~10%, B2O3 18%~25%, CaO 0.5%~4%, MgO 0~2%, ZnO 2%~6%, BaO 0~1%, Na2O 3%~7%, K2O 4%~8%, Li2O 0~1.5%, and ZrO2 0~2%.

[0026] The low expansion frit is made from the following components: SiO2 48%~55%, Al2O3 12%~18%, B2O3 3%~8%, CaO 8%~14%, MgO 3%~7%, ZnO 0~3%, BaO 0~2%, Na2O 1%~4%, K2O 3%~6%, Li2O 1%~3%, ZrO2 0~4%.

[0027] Specifically, this embodiment further precisely defines the chemical composition of the high-boron frit and the low-expansion frit, achieving a second leap in chemical stability and cloud-like kiln transformation artistic effects.

[0028] By strictly limiting the B2O3 content of the high-boron melt to 18%~25%, reducing the total alkali metal content (Na2O+K2O) to below 10%, and BaO to ≤1%, and controlling the thermal expansion coefficient of the low-expansion melt to a low level, the final glass phase ratio of the glaze layer can be further increased to over 90%, and free alkali metals, calcium, barium and other easily migrating ions are locked into the borosilicate network structure to the greatest extent.

[0029] Furthermore: The raw material components of the high boron ingot also include: 0.8%~2.5% phosphorus source compound and 0.3%~1.2% cerium oxide. The phosphorus source compound is selected from ammonium dihydrogen phosphate or calcium phosphate.

[0030] The raw material composition of low expansion ingots also includes 1.0% to 3.0% calcium fluoride.

[0031] Specifically, this embodiment further introduces a phosphorus source compound + cerium oxide into the high-boron molten metal and calcium fluoride into the low-expansion molten metal, resulting in the following three technical effects: P at high temperature 5+ Ce4 released with kaolin A + / La 3+ In-situ generation of CePO4 / LaPO4 monazite microcrystals with sizes of 20–80 nm, V 5+ / V 4+ Selectively adsorbed around the microcrystals, forming extremely fine "vanadium blue / vanadium yellow rings", giving it a high-end "rabbit hair + misty flower" texture to the naked eye.

[0032] F- By reducing the viscosity of the glaze melt by approximately 28% at 1200℃, and combining this with the microbubble channels generated by the ignition loss of porcelain clay B, the maximum stretching length of a single cloud-like pattern is increased from 3-6 cm in the ordinary formula to 10-18 cm, presenting an extremely ethereal feel reminiscent of ink wash painting; simultaneously, F - The glaze surface is induced to form a nanoscale uneven structure, causing light to be diffusely reflected through a velvety surface, resulting in a comfortable visual experience; Trace Ce 4+ / Ce 3+ Price change and F - The residue causes the glaze to form a dual-mode glass network (high boron region + cerium-fluorine region), which can increase the Vickers hardness from 6.8 GPa to 7.3~7.6 GPa. After testing in a 200 rpm dishwasher, the gloss retention rate can be stabilized at 99.0%~99.6%, with almost no perceptible changes, achieving an unprecedented level of "never losing gloss" in the industry.

[0033] Furthermore, porcelain clay A is Guizhou kaolin, and porcelain clay B is Jiepai kaolin.

[0034] This embodiment also provides a preparation method for preparing a highly chemically stable cloud-shaped glaze as described in any one of the above embodiments. The preparation method includes the following steps: S1. Weigh the glaze components of the high chemical stability cloud kiln-transformed glaze according to the weight parts, mix them, add the dispersion medium and ball milling medium, and then ball mill to obtain the glaze slurry.

[0035] S2. Apply the glaze slurry to the surface of the porcelain body to obtain the glaze body.

[0036] S3. Dry the glaze body to a moisture content of ≤1% and keep it at 100~130℃ for 0.5~2 hours.

[0037] S4. The glaze body obtained in step S3 is fired in an oxidizing atmosphere. After firing, a highly chemically stable cloud-shaped glaze is obtained and applied to the ceramic surface.

[0038] Further, in step S1, the dispersion medium is a mixture of water and a dispersant, the dispersant being selected from polycarboxylate or sodium tripolyphosphate, and the amount added is 0.1% to 0.4% of the total mass of the glaze; the ball milling medium is alumina balls or zirconia balls, wherein the mass ratio of glaze, milling balls, and dispersion medium is 1:(1.8 to 2.2):(0.65 to 0.75), the ball milling time is 18 to 36 hours, and the average particle size of the resulting glaze slurry is 40 to 60 μm.

[0039] Furthermore, in step S2, the glazing method is immersion glazing, glazing pouring glazing, or glazing spraying glazing, and the glaze layer thickness is 0.25~0.45mm.

[0040] Furthermore, in step S4, the firing temperature is 1190~1230℃, and the highest temperature is held for 15~50 minutes. The heating rate is ≤120℃ / h before 1000℃ and ≤80℃ / h after 1000℃.

[0041] Among them, the limitation of glaze preparation and glazing parameters ensures that the frit, porcelain clay A / B, and vanadium-titanium colorant are highly uniformly distributed in the glaze layer, avoiding the cloudiness or fragmentation caused by local component segregation; at the same time, the thickness is strictly controlled within 0.45 mm to ensure that a single layer of glaze can still quickly form a sufficient liquid phase at around 1200℃, achieving the optimal time window for the synergistic phase separation of phosphorus-cerium-vanadium microcrystal nuclei and fluorine viscosity reduction.

[0042] The defined firing temperature profile and precise firing temperature range of 1190~1230℃ allow porcelain clay B to slowly burn off organic carbon at 800~950℃, forming uniform microbubble channels, while simultaneously preventing excessively rapid heating during the high-temperature stage from causing F... - V 4+ Excessive diffusion ensures the complete preservation of the diffuse reflection structure of rabbit hair filaments and silk.

[0043] Furthermore, the high boron frit is prepared by the following steps: after the raw material components of the high boron frit are mixed evenly, it is melted at 1200~1250℃ for 2~3.5 hours. During the melting process, a weak oxidizing atmosphere is maintained. After melting, the frit is quenched in water to form frit particles. After drying, it is ball-milled until the residue on a 325-mesh sieve is ≤1.5%.

[0044] Furthermore, the low-expansion frit is prepared by the following steps: after the raw materials and components of the low-expansion frit are mixed evenly, it is melted at 1220~1300℃ for 2~3 hours. During the melting process, an oxidizing atmosphere is maintained. After melting, the frit is quenched in water to form frit particles. After drying, it is ball-milled until the residue on a 325-mesh sieve is ≤1.0%, and the frit is obtained.

[0045] Specifically, the high-boron frit is melted at a temperature of 1200~1250℃ in a weak oxidizing atmosphere, which ensures that B2O3 reacts fully without volatilizing in large quantities (volatilization rate <4%). At the same time, the phosphorus source compound decomposes completely at this temperature and generates monazite microcrystalline precursors in situ with CeO2 and rare earth ions, providing the most stable nucleus source for the subsequent "rabbit's fur" glaze.

[0046] The melting temperature of the low-expansion frit is increased to 1220~1300℃, and calcium fluoride can be added after the melt is clarified, which ensures that the volatility of CaF2 is controlled within 10% and that it is fully integrated into the glass phase, maximizing the effects of viscosity reduction and nano-protrusion formation.

[0047] Specific embodiments are provided below. These embodiments are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way.

[0048] Example 1 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0049] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0050] Glaze ingredients: 2.00 kg high boron frit, 1.50 kg low expansion frit, 2.00 kg potassium feldspar, 2.00 kg quartz, 0.30 kg calcined talc, 0.40 kg calcined zinc oxide, 0.30 kg Guizhou clay, 0.50 kg Jiepai clay, 0.50 kg titanium dioxide, 50 g cobalt blue + manganese red composite ceramic colorant, and 100 g vanadium pentoxide.

[0051] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0052] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.5 seconds, resulting in an average weight gain of 9.4–10.1 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average temperature was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. After firing, 50 samples showed no defects such as pinholes, glaze rolling, or cracking.

[0053] The test items and test data of the prepared samples are shown in Table 1 below: Example 2 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0054] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0055] Glaze ingredients: 2.70 kg high boron frit, 1.80 kg low expansion frit, 1.00 kg potassium feldspar, 1.50 kg quartz, 0.30 kg calcined talc, 0.70 kg calcined zinc oxide, 0.40 kg Guizhou clay, 1.00 kg Jiepai clay, 0.70 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 200 g vanadium pentoxide.

[0056] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0057] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.7 seconds, resulting in an average weight gain of 9.9–10.6 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average temperature was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. After firing, 50 samples showed no defects such as pinholes, glaze rolling, or cracking.

[0058] The test items and test data of the prepared samples are shown in Table 2 below: Example 3 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0059] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0060] Glaze ingredients: 1.50 kg high boron frit, 2.00 kg low expansion frit, 1.00 kg potassium feldspar, 1.00 kg quartz, 0.60 kg calcined talc, 0.70 kg calcined zinc oxide, 0.30 kg Guizhou clay, 0.60 kg Jiepai clay, 0.50 kg titanium dioxide, 900 g cobalt blue + manganese red composite ceramic colorant, and 300 g vanadium pentoxide.

[0061] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0062] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.8 seconds, resulting in an average weight gain of 9.6–10.3 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average temperature was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. After firing, 50 samples showed no defects such as pinholes, glaze rolling, or cracking.

[0063] The test items and test data of the prepared samples are shown in Table 3 below: Example 4 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0064] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0065] Glaze ingredients: 2.70 kg high boron frit, 1.80 kg low expansion frit, 1.00 kg potassium feldspar, 1.50 kg quartz, 0.30 kg calcined talc, 0.30 kg calcined zinc oxide, 0.50 kg Guizhou clay, 0.50 kg Jiepai clay, 0.60 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 200 g vanadium pentoxide.

[0066] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0067] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.6 seconds, resulting in an average weight gain of 9.5–10.2 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average temperature was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. After firing, 50 samples showed no defects such as pinholes, glaze rolling, or cracking.

[0068] The test items and test data of the prepared samples are shown in Table 4 below: Example 5 8.00 kg of high boron frit was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use.

[0069] Chemical composition: SiO2 44.7%, Al2O3 8.4%, B2O3 23.8%, CaO 2.3%, ZnO 4.8%, Na2O 6.2%, K2O 7.4%, Li2O 0.8%, NH4H2PO4 1.8%, nano CeO2 0.8%.

[0070] 6.00 kg of low-expansion frit was melted, and after the melt was clarified at 1270℃, calcium fluoride was added and kept at that temperature for 30 min. Then, the temperature was raised to 1275℃ and kept at that temperature for 2 h. The melt was then water-quenched, dried, and ball-milled for later use.

[0071] Chemical composition: SiO2 52.9%, Al2O3 16.2%, B2O3 4.9%, CaO 12.2%, MgO 5.6%, ZnO 1.4%, Li2O 2.8%, Na2O 2.1%, K2O 3.5%, CaF2 2.0%.

[0072] Glaze ingredients: 2.50 kg high boron frit, 1.80 kg low expansion frit, 1.20 kg potassium feldspar, 1.80 kg quartz, 0.40 kg calcined talc, 0.50 kg calcined zinc oxide, 0.50 kg Guizhou clay, 0.70 kg Jiepai clay, 0.60 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 200 g vanadium pentoxide.

[0073] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0074] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.7 seconds, resulting in an average weight gain of 9.8–10.5 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average temperature was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. After firing, 50 samples showed no defects such as pinholes, glaze rolling, or cracking.

[0075] The test items and test data of the prepared samples are shown in Table 5 below: Comparative Example 1 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0076] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0077] Glaze ingredients: 2.50 kg high boron frit, 1.80 kg low expansion frit, 1.20 kg potassium feldspar, 1.80 kg quartz, 0.40 kg calcined talc, 0.50 kg calcined zinc oxide, 0.80 kg Guizhou clay, 0.70 kg Jiepai clay, 0.60 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 200 g vanadium pentoxide.

[0078] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0079] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.7 seconds, resulting in an average weight gain of 9.9–10.6 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The samples were fired in a gas-fired shuttle kiln under an oxidizing atmosphere. The average firing rate was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. No obvious firing defects were found in the 50 samples after exiting the kiln.

[0080] The test items and test data of the prepared samples are shown in Table 6 below: Comparative Example 2 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0081] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0082] Glaze ingredients: 2.50 kg high boron frit, 1.80 kg low expansion frit, 1.20 kg potassium feldspar, 1.80 kg quartz, 1.80 kg calcined talc, 0.50 kg calcined zinc oxide, 0.50 kg Guizhou clay, 0.70 kg Jiepai clay, 0.60 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 200 g vanadium pentoxide.

[0083] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0084] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.7 seconds, resulting in an average weight gain of 9.8–10.5 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average temperature was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. Slight glaze runners were observed after the kiln was removed from the heat.

[0085] The test items and test data of the prepared samples are shown in Table 7 below: Comparative Example 3 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0086] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0087] Glaze ingredients: 0.50 kg high boron frit, 1.80 kg low expansion frit, 1.20 kg potassium feldspar, 1.80 kg quartz, 0.40 kg calcined talc, 0.50 kg calcined zinc oxide, 0.50 kg Guizhou clay, 0.70 kg Jiepai clay, 0.60 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 200 g vanadium pentoxide.

[0088] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0089] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.7 seconds, resulting in an average weight gain of 9.7–10.4 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The samples were fired in a gas-fired shuttle kiln under an oxidizing atmosphere. The average firing rate was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. No obvious firing defects were found in the 50 samples after exiting the kiln.

[0090] The test items and test data of the prepared samples are shown in Table 8 below: Comparative Example 4 15.00 kg of high-boron ingot was melted, held at 1240℃ for 2 h 30 min, water-quenched, dried, and ball-milled for later use. The high-boron ingot contained 45.5% SiO2, 8.4% Al2O3, 23.8% B2O3, 2.3% CaO, 4.8% ZnO, 6.2% Na2O, 7.4% K2O, and 0.8% Li2O.

[0091] 15.00 kg of low-expansion frit was melted, held at 1275℃ for 2 h 20 min, water-quenched, dried, and ball-milled for later use. The low-expansion frit contained 53.1% SiO2, 16.2% Al2O3, 4.9% B2O3, 12.8% CaO, 5.6% MgO, 1.4% ZnO, 2.8% Li2O, 2.1% Na2O, and 3.5% K2O.

[0092] Glaze ingredients: 2.50 kg high boron frit, 1.80 kg low expansion frit, 1.20 kg potassium feldspar, 1.80 kg quartz, 0.40 kg calcined talc, 0.50 kg calcined zinc oxide, 0.50 kg Guizhou clay, 0.70 kg Jiepai clay, 0.60 kg titanium dioxide, 300 g cobalt blue + manganese red composite ceramic colorant, and 1 kg vanadium pentoxide.

[0093] Add 20.0 kg of zirconia balls, 6.80 kg of water, and 30 g of sodium tripolyphosphate to a ball mill and mill for 28 h.

[0094] Fifty unglazed stoneware round cups were selected. They were immersed in glaze for 3.7 seconds, resulting in an average weight gain of 9.9–10.5 g per cup after glazing. They were then dried in a 120℃ oven for 55 minutes. After drying, they were placed in an 80℃ oven. 3 The kiln was gas-fired and fired in an oxidizing atmosphere. The average firing rate was 108℃ / h before reaching 1000℃ and 71℃ / h after reaching 1000℃. The highest temperature was 1215℃, which was held for 38 minutes, followed by natural cooling. After firing, the glaze surface showed obvious coarse net-like patterns.

[0095] The test items and test data of the prepared samples are shown in Table 9 below: As can be seen from the above embodiments and comparative examples: Examples 1-5 all met the 200 rpm dishwasher test standard level 5 (without any change), with a gloss retention rate of 99.1%-99.6% and a lead leaching amount of 0.029-0.041 mg / L, which is far superior to conventional kiln-transformed glazes. This fully demonstrates that the component range defined by the implementation method can stably achieve extremely high chemical stability and clear cloud kiln-transformation effect under single-layer glaze conditions.

[0096] In Example 5, under the action of phosphorus source + cerium oxide + calcium fluoride, the gloss retention rate was further improved to 99.6%, and fine rabbit hair-like patterns appeared on the glaze surface, resulting in optimal decorative properties and corrosion resistance.

[0097] The addition amounts of calcined zinc oxide, calcite, high-boron frit, and vanadium pentoxide in Comparative Examples 1 to 4 exceeded the specified ranges, resulting in either severe failure of the 200 rpm dishwasher (level 1 to 2) or destruction of the cloud effect. This fully demonstrates that the limitation of each component and its range in this embodiment has significant technical effects and is necessary.

[0098] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of the present invention. The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the technical scope disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be within the scope of protection of the present invention.

Claims

1. A highly chemically stable cloud-shaped kiln-transformed glaze, characterized in that, The product is made from the following components by weight: 20-27 parts high-boron frit, 15-20 parts low-expansion frit, 10-20 parts potassium feldspar, 15-25 parts quartz, 3-6 parts calcined talc, 3-7 parts calcined zinc oxide, 3-7 parts kaolin A, 5-10 parts kaolin B, 4-7 parts titanium dioxide, 0.1-12 parts ceramic colorant, and 1-3 parts vanadium pentoxide. Kaolin A is selected from kaolin containing 0.05-0.4 wt% rare earth oxides, and kaolin B is selected from large-particle suspended kaolin with a 325-mesh sieve residue ≤0.1% and a loss on ignition of 5%-8%.

2. The high chemical stability cloud-shaped kiln-transformed glaze according to claim 1, characterized in that, By weight percentage: The high-boron frit is composed of the following components: SiO2 42%~48%, Al2O3 6%~10%, B2O3 18%~25%, CaO 0.5%~4%, MgO 0~2%, ZnO 2%~6%, BaO 0~1%, Na2O 3%~7%, K2O 4%~8%, Li2O 0~1.5%, ZrO2 0~2%; The low-expansion frit is made of the following components: SiO2 48%~55%, Al2O3 12%~18%, B2O3 3%~8%, CaO 8%~14%, MgO 3%~7%, ZnO 0~3%, BaO 0~2%, Na2O 1%~4%, K2O 3%~6%, Li2O 1%~3%, ZrO2 0~4%.

3. The high chemical stability cloud-shaped glaze according to claim 2, characterized in that: The raw material composition of the high-boron fused block further includes: 0.8%~2.5% phosphorus source compound and 0.3%~1.2% cerium oxide, wherein the phosphorus source compound is selected from ammonium dihydrogen phosphate or calcium phosphate; The raw material composition of the low expansion melt also includes 1.0% to 3.0% calcium fluoride.

4. The high chemical stability cloud-shaped glaze according to any one of claims 1 to 3, characterized in that, The porcelain clay A is Guizhou kaolin, and the porcelain clay B is Jiepai kaolin.

5. A preparation method, characterized in that, The method for preparing the highly chemically stable cloud-shaped kiln-transformed glaze as described in any one of claims 1 to 4 comprises the following steps: S1. Weigh the glaze components of the high chemical stability cloud kiln-transformed glaze according to the weight parts, mix them, add the dispersion medium and ball milling medium, and then ball mill to obtain the glaze slurry; S2. Apply the glaze slurry to the surface of the porcelain body to obtain a glaze body; S3. Dry the glaze body to a moisture content of ≤1%, and keep it at 100~130℃ for 0.5~2 hours; S4. The glaze body obtained in step S3 is fired in an oxidizing atmosphere. After firing, a highly chemically stable cloud-shaped glaze is obtained and applied to the ceramic surface.

6. The preparation method according to claim 5, characterized in that, In step S1, the dispersion medium is a mixture of water and a dispersant, the dispersant being selected from polycarboxylate or sodium tripolyphosphate, and the amount added is 0.1% to 0.4% of the total mass of the glaze; the ball milling medium is alumina balls or zirconia balls, wherein the mass ratio of glaze, milling balls, and dispersion medium is 1:(1.8 to 2.2):(0.65 to 0.75), the ball milling time is 18 to 36 hours, and the average particle size of the resulting glaze slurry is 40 to 60 μm.

7. The preparation method according to claim 5, characterized in that, In step S2, the glazing method is immersion glazing, glazing pouring glazing or glazing spraying glazing, and the glaze layer thickness is 0.25~0.45mm.

8. The preparation method according to claim 5, characterized in that, In step S4, the firing temperature is 1190~1230℃, and the highest temperature is held for 15~50 minutes. The heating rate is ≤120℃ / h before 1000℃ and ≤80℃ / h after 1000℃.

9. The preparation method according to claim 5, characterized in that, The high-boron frit is prepared by the following steps: after the raw material components of the high-boron frit are mixed evenly, it is melted at 1200~1250℃ for 2~3.5 hours. During the melting process, a weak oxidizing atmosphere is maintained. After melting, the frit is quenched in water to form frit particles. After drying, it is ball-milled until the residue on a 325-mesh sieve is ≤1.5%.

10. The preparation method according to claim 5, characterized in that, The low-expansion frit is prepared by the following steps: after the raw materials and components of the low-expansion frit are mixed evenly, it is melted at 1220~1300℃ for 2~3 hours. During the melting process, an oxidizing atmosphere is maintained. After melting, the frit is quenched in water to form frit particles. After drying, it is ball-milled until the residue on a 325-mesh sieve is ≤1.0%.

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