A lead-free, high-temperature-resistant, silver-gray glaze with metallic luster and its application

Abstract

The present invention belongs to the technical field of ceramic glazes, specifically relating to a lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster and its application. The silver-gray glaze comprises, by weight, 31.52% to 32.20% of low-expansion coefficient frit; 19.31% to 19.41% of high-boron frit; 4.60% to 4.70% of Al2O3; 23.36% to 23.86% of potassium feldspar; 5.08% to 5.32% of MnO2; 4.77% to 4.83% of CuO; 2.58% to 2.63% of SrCO3; 1.64% to 1.88% of CaCO3; 3.54% to 3.62% of ZrO2; and 2.86% to 2.94% of Li2CO3. The glaze is lead-free, high-temperature-resistant, and can be used to produce a silver-gray glaze surface with a metallic luster. The preparation process does not require vacuum operation, resulting in low cost and excellent product performance.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic glazes, and in particular relates to a lead-free, high-temperature-resistant, silver-grey glaze with metallic luster and an application thereof. Background Art

[0002] Glaze is a colorless or colored glassy thin layer covering the surface of ceramic products. It is made by mixing mineral raw materials (feldspar, quartz, talc, kaolin, etc.) and raw materials in a certain proportion (some raw materials can be made into frits first), grinding them into glaze slurry, applying them to the surface of the body, and calcining them at a certain temperature.

[0003] The continuous advancement of science and technology has led to people's pursuit of a higher quality of life. Metallic luster glazes show unique artistic effects and are highly anticipated by consumers. At present, there are three main preparation processes for imitation metallic luster glazes at home and abroad: (1) directly sputtering a molten metal coating on the ceramic body; (2) spraying metal oxide powder on the surface of the ceramic body and reducing and sintering; (3) developing a glaze formula with a certain chemical composition, and obtaining a ceramic glaze product with metallic luster through processes such as glazing and high-temperature calcination. However, the first two processes are not glazes in the strict sense. Their preparation effects do not form a glassy layer, but only a hard bond between the metal oxide and the ceramic body. The specific implementation process needs to be operated under vacuum conditions, which is difficult, not resistant to high temperatures, and has poor durability, and its application is very limited. The third process can be implemented in an ordinary air atmosphere, and the production operation is simple and convenient, and it is the most widely used in practice.

[0004] Currently, all metallic glazes on the market contain lead. Lead oxide can make the metallic glaze brighter, smoother, and more uniform. However, lead is a toxic heavy metal that not only pollutes the environment but also affects the health of producers and users, limiting its widespread application. Furthermore, commercially available metallic glazes cannot withstand firing temperatures exceeding 1100°C, limiting their practical application. Furthermore, the scarcity of various metallic glaze colors is a bottleneck that the glaze industry urgently needs to address.

[0005] Therefore, preparing a glaze formula that is high-temperature resistant, lead-free, and has a metallic luster is a difficult problem that needs to be solved urgently in the ceramic and glaze industries. Summary of the Invention

[0006] The present invention aims to solve the above technical problems and provide a lead-free, high-temperature resistant, silver-gray glaze with metallic luster and its application. The obtained ceramic glaze is lead-free, high-temperature resistant to 1200-1240°C, and can produce a silver-gray glaze with metallic luster, high surface hardness and good stability.

[0007] The technical solution of the present invention is:

[0008] A lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster, the chemical components of which, by weight percentage, include:

[0009] Low expansion coefficient frit 31.52%~32.20%; high boron frit 19.31%~19.41%; Al2O3 4.60%~4.70%; potassium feldspar 23.36%~23.86%; MnO2 5.08%~5.32%; CuO 4.77%~4.83%; SrCO3 2.58%~2.63%; CaCO3 1.64%~1.88%; ZrO2 3.54%~3.62%; Li2CO3 2.86%~2.94%.

[0010] Furthermore, the chemical components of the low expansion coefficient frit include, by weight percentage: Na2O 3.09%; K2O 3.40%; CaO 9.02%; MgO 0.48%; Li2O 4.31%; ZnO 2.34%; B2O3 12.26%; Al2O3 10.13%; and SiO2 54.97%.

[0011] Furthermore, the chemical components of the high-boron frit include, by weight percentage: Na2O 10.60%; B2O3 23.95%; SiO2 65.45%.

[0012] The application of the lead-free, high-temperature resistant, silver-gray glaze with metallic luster described in the present invention is specifically as follows: glazing the surface of a ceramic body, wherein the glaze is the lead-free, high-temperature resistant, silver-gray glaze with metallic luster. After firing, a ceramic product is obtained, the glaze surface of which has a metallic luster and a significant silver-gray color.

[0013] The application of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster of the present invention comprises the following steps:

[0014] 1) Prepare a stabilizing system solution: Weigh water and defoamer separately, mix well, then add adhesive, continue mixing well, add dispersant and preservative, and then mix well to form a stabilizing system solution;

[0015] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.35-1.38 g / cm 3 Black-grey glaze slurry;

[0016] 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry;

[0017] 4) calcining the green body obtained from step 3) in an oxidizing atmosphere at 1200-1240° C. to obtain a silver-grey glaze with metallic luster.

[0018] Furthermore, the defoaming agent is a polyether defoaming agent.

[0019] Furthermore, the adhesive is a polyurethane adhesive.

[0020] Furthermore, the dispersant is sodium tripolyphosphate.

[0021] Furthermore, the preservative is benzisothiazolinone.

[0022] The beneficial effects of the present invention are:

[0023] The present invention uses low expansion coefficient frit, high boron frit, potassium feldspar and Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 as raw materials, and through optimized combination, obtains the chemical composition according to weight percentage: low expansion coefficient frit 31.52% to 32.20%; high boron frit 19.31% to 19.41%; Al2O3 4.60% to 4.70%; potassium feldspar 23.36% to 23.86%; MnO2 5.08% to 5.32%; CuO4 .77%~4.83%; SrCO32.58%~2.63%; CaCO31.64%~1.88%; ZrO23.54%~3.62%; Li2CO32.86%~2.94% ceramic glaze, which is lead-free and high-temperature resistant. The above glaze can be used to prepare a silver-gray metal ceramic glaze with metallic luster, uniformity, high surface hardness and good stability. The entire preparation process does not need to be operated under vacuum conditions, and has the characteristics of simple production equipment, low preparation cost and good product performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a real-life rendering of Example 1 of the present invention;

[0025] Figure 2 This is a real-life rendering of Example 2 of the present invention;

[0026] Figure 3 This is a real-life rendering of Example 3 of the present invention;

[0027] Figure 4 This is a real-life rendering of Example 4 of the present invention;

[0028] Figure 5 This is a real-life rendering of Example 5 of the present invention;

[0029] Figure 6 This is a real-life rendering of Comparative Example 1 of the present invention;

[0030] Figure 7 This is a real-life rendering of Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0031] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0032] Example 1

[0033] A lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster, the chemical components of which, by weight percentage, include: 31.69% of low-expansion coefficient frit; 19.41% of high-boron frit; 4.62% of Al2O3; 23.48% of potassium feldspar; 5.14% of MnO2; 4.78% of CuO; 2.59% of SrCO3; 1.84% of CaCO3; 3.59% of ZrO2; and 2.86% of Li2CO3.

[0034] The application of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster described in this embodiment includes the following steps:

[0035] 1) Prepare a stabilizing system solution: Weigh 62.082 g of water and 0.031 g of defoamer, mix well, then add 1.2935 g of adhesive. Continue mixing, then add 0.771 g of dispersant and 0.771 g of preservative, and mix well to form a stabilizing system solution.

[0036] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.36g / cm 3 Black-grey glaze slurry;

[0037] 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry;

[0038] 4) calcining the green body after drying in step 3) at 1200° C. in an oxidizing atmosphere to obtain a silver-grey glaze with metallic luster.

[0039] Example 2

[0040] A lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster comprises, by weight, 32.20% of a low-expansion coefficient frit; 19.31% of a high-boron frit; 4.61% of Al2O3; 23.36% of potassium feldspar; 5.08% of MnO2; 4.77% of CuO; 2.58% of SrCO3; 1.64% of CaCO3; 3.58% of ZrO2; and 2.87% of Li2CO3.

[0041] The application of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster described in this embodiment includes the following steps:

[0042] 1) Prepare a stabilizing system solution: Weigh 62.082 g of water and 0.031 g of defoamer, mix well, then add 1.2935 g of adhesive. Continue mixing, then add 0.771 g of dispersant and 0.771 g of preservative, and mix well to form a stabilizing system solution.

[0043] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.35g / cm 3 Black-grey glaze slurry;

[0044] 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry;

[0045] 4) calcining the green body obtained by drying in step 3) at 1240° C. in an oxidizing atmosphere to obtain a silver-grey glaze with metallic luster.

[0046] Example 3

[0047] A lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster comprises, by weight, 31.84% of a low-expansion coefficient frit; 19.35% of a high-boron frit; 4.60% of Al2O3; 23.37% of potassium feldspar; 5.32% of MnO2; 4.77% of CuO; 2.63% of SrCO3; 1.64% of CaCO3; 3.54% of ZrO2; and 2.94% of Li2CO3.

[0048] The application of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster described in this embodiment includes the following steps:

[0049] 1) Weigh 62.082 g of water and 0.031 g of defoamer, mix well, add 1.2935 g of adhesive, continue mixing well, add 0.771 g of dispersant and 0.771 g of preservative, and then mix well to form a stable system solution;

[0050] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.38g / cm 3 Black-grey glaze slurry;

[0051] 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry;

[0052] 4) calcining the green body obtained by drying in step 3) at 1210° C. in an oxidizing atmosphere to obtain a silver-grey glaze with metallic luster.

[0053] Example 4

[0054] A lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster comprises, by weight, 31.52% of a low-expansion coefficient frit; 19.31% of a high-boron frit; 4.60% of Al2O3; 23.72% of potassium feldspar; 5.08% of MnO2; 4.83% of CuO; 2.58% of SrCO3; 1.88% of CaCO3; 3.61% of ZrO2; and 2.87% of Li2CO3.

[0055] The application of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster described in this embodiment includes the following steps:

[0056] 1) Weigh 62.082 g of water and 0.031 g of defoamer, mix well, add 1.2935 g of adhesive, continue mixing well, add 0.771 g of dispersant and 0.771 g of preservative, and then mix well to form a stable system solution;

[0057] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.36g / cm 3 Black-grey glaze slurry;

[0058] 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry;

[0059] 4) calcining the green body obtained by drying in step 3) at 1220° C. in an oxidizing atmosphere to obtain a silver-grey glaze with metallic luster.

[0060] Example 5

[0061] A lead-free, high-temperature-resistant, silver-gray glaze with a metallic luster, the chemical components of which, by weight percentage, include: 31.52% of low-expansion coefficient frit; 19.31% of high-boron frit; 4.70% of Al2O3; 23.86% of potassium feldspar; 5.08% of MnO2; 4.77% of CuO; 2.58% of SrCO3; 1.64% of CaCO3; 3.62% of ZrO2; and 2.92% of Li2CO3.

[0062] The application of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster described in this embodiment includes the following steps:

[0063] 1) Weigh 62.082 g of water and 0.031 g of defoamer, mix well, add 1.2935 g of adhesive, continue mixing well, add 0.771 g of dispersant and 0.771 g of preservative, and then mix well to form a stable system solution;

[0064] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.37g / cm 3 Black-grey glaze slurry;

[0065] 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry;

[0066] 4) calcining the green body obtained by drying in step 3) at 1230° C. in an oxidizing atmosphere to obtain a silver-grey glaze with metallic luster.

[0067] In the above embodiments, the low expansion coefficient frit, high boron frit, defoamer, adhesive, dispersant and preservative are all commercially available products.

[0068] The chemical components of the low expansion coefficient frit include, by weight percentage, 3.09% Na2O, 3.40% K2O, 9.02% CaO, 0.48% MgO, 4.31% Li2O, 2.34% ZnO, 12.26% B2O3, 10.13% Al2O3, and 54.97% SiO2.

[0069] The chemical components of the high-boron frit include, by weight percentage: Na2O 10.60%, B2O3 23.95%, and SiO2 65.45%.

[0070] The defoaming agent is a polyether defoaming agent, specifically a GPE defoaming agent; the adhesive is a polyurethane adhesive; the dispersant is sodium tripolyphosphate; and the preservative is benzisothiazolinone.

[0071] In order to illustrate the technical effect of the present invention, the inventors set up a comparative example and conducted comparative tests as follows:

[0072] Comparative Example 1: The difference from Example 1 is that its chemical composition and weight ratio are different (no ZrO2). Specifically:

[0073] A glaze, the chemical components of which are calculated by weight percentage: 32.87% of low expansion coefficient frit; 20.13% of high boron frit; 4.79% of Al2O3; 24.35% of potassium feldspar; 5.33% of MnO2; 4.96% of CuO; 2.69% of SrCO3; 1.91% of CaCO3; and 2.97% of Li2CO3.

[0074] The application of the glaze described in this comparative example comprises the following steps:

[0075] 1) Prepare a stabilizing system solution: Weigh 62.082 g of water and 0.031 g of defoamer, mix well, then add 1.2935 g of adhesive. Continue mixing, then add 0.771 g of dispersant and 0.771 g of preservative, and mix well to form a stabilizing system solution.

[0076] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.36g / cm 3 glaze slurry;

[0077] 3) Pass the glaze slurry from step 2) through a 200-mesh sieve, apply it on the surface of the body, and let it dry;

[0078] 4) calcining the green body after drying in step 3) at 1200° C. in an oxidizing atmosphere to obtain a glaze surface.

[0079] Comparative Example 2: The difference from Example 1 is that its chemical composition and weight ratio are different (does not contain Li2CO3). Specifically:

[0080] A glaze, the chemical components of which are calculated by weight percentage: 32.62% of low expansion coefficient frit; 19.98% of high boron frit; 4.76% of Al2O3; 24.17% of potassium feldspar; 5.29% of MnO2; 4.92% of CuO; 2.67% of SrCO3; 1.89% of CaCO3; and 3.70% of ZrO2.

[0081] The application of the glaze described in this comparative example comprises the following steps:

[0082] 1) Prepare a stabilizing system solution: Weigh 62.082 g of water and 0.031 g of defoamer, mix well, then add 1.2935 g of adhesive. Continue mixing, then add 0.771 g of dispersant and 0.771 g of preservative, and mix well to form a stabilizing system solution.

[0083] 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, and ZrO2 to the stabilization system solution of step 1) in sequence, and stir evenly to obtain a solution with a specific gravity of 1.36 g / cm 3 glaze slurry;

[0084] 3) Pass the glaze slurry from step 2) through a 200-mesh sieve, apply it on the surface of the body, and let it dry;

[0085] 4) calcining the green body after drying in step 3) at 1200° C. in an oxidizing atmosphere to obtain a glaze surface.

[0086] The glazes prepared in the examples and comparative examples were checked and the results were as follows: Figure 1-Figure 7 As shown:

[0087] Figure 1-5 The actual effect pictures of Examples 1-5 are respectively shown. It can be seen that the glaze surfaces of Examples 1-5 are uniform, with obvious silver-gray color, strong metallic luster, low fluidity, and good overall effect.

[0088] Figure 6 This is the actual effect diagram of Comparative Example 1. Figure 7 This is the actual effect diagram of Comparative Example 2. Figure 1 and Figure 6 Comparison shows that the formula of Comparative Example 1, compared with Example 1, does not contain ZrO2, and its effect is: strong metallic luster and strong golden metallic texture, but the silver-gray color is not significant, and the upper part of the glaze is uneven. Comparative Example 2, compared with Example 1, does not contain Li2CO3, and its effect is: significant silver-gray color, but slightly weak metallic luster, and due to the excessive fluidity of the glaze, the upper part is uneven. Therefore, Examples 1-5 are the products required by the present invention. The glaze has a strong metallic luster, a significant silver-gray color, is lead-free and harmless to human health, and is popular with the public.

[0089] The gloss performance test of the present invention is:

[0090] The gloss value of the sample at 60° was obtained by testing using a 3nh gloss meter HG60S. The results are shown in Table 1. A larger ratio indicates a higher gloss, and a smaller ratio indicates a lower gloss.

[0091] Table 1 Glossiness performance parameters of examples and comparative examples

[0092]

[0093] The above description is a detailed description of the preferred embodiments of the invention, but the embodiments are not intended to limit the scope of the patent application of the present invention. Any equivalent changes or modifications completed under the technical spirit suggested by the present invention should fall within the patent scope covered by the present invention.

Claims

1. A lead-free, high-temperature-resistant, silver-gray glaze with metallic luster, characterized in that: Its chemical components by weight percentage include: Low expansion coefficient frit 31.52% to 32.20%; high boron frit 19.31% to 19.41%; Al2O3 4.60% to 4.70%; potassium feldspar 23.36% to 23.86%; MnO2 5.08% to 5.32%; CuO 4.77% to 4.83%; SrCO3 2.58% to 2.63%; CaCO3 1.64% to 1.88%; ZrO2 3.54% to 3.62%; Li2CO3 2.86% to 2.94%; The chemical components of the low expansion coefficient frit include, by weight percentage: Na2O 3.09%; K2O 3.40%; CaO 9.02%; MgO 0.48%; Li2O 4.31%; ZnO 2.34%; B2O3 12.26%; Al2O3 10.13%; SiO2 54.97%; The chemical components of the high-boron frit include, by weight percentage: Na2O 10.60%, B2O3 23.95%, and SiO2 65.45%.

2. Use of the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster according to claim 1 in the preparation of ceramic products, characterized in that: The surface of the ceramic body is glazed with the lead-free, high-temperature-resistant, silver-grey glaze having a metallic luster. After firing, a ceramic product is obtained, the glaze surface of which has a metallic luster and a significant silver-grey color.

3. A method for preparing the lead-free, high-temperature-resistant, silver-gray glaze with metallic luster according to claim 1, characterized in that: The following steps are involved: 1) Prepare a stabilizing system solution: Weigh water and defoamer separately, mix well, then add adhesive, continue mixing well, add dispersant and preservative, and then mix well to form a stabilizing system solution; 2) Add low expansion coefficient frit, high boron frit, potassium feldspar, Al2O3, MnO2, CuO, SrCO3, CaCO3, ZrO2, Li2CO3 to the stabilization system solution of step 1) in sequence, stir evenly to obtain a specific gravity of 1.35-1.38 g / cm 3 Black-grey glaze slurry; 3) Pass the black-gray glaze slurry from step 2) through a 200-mesh sieve, apply it to the surface of the body, and let it dry; 4) calcining the green body obtained from step 3) in an oxidizing atmosphere at 1200-1240° C. to obtain a silver-grey glaze with metallic luster.

4. The preparation method according to claim 3, characterized in that The defoamer is a polyether defoamer.

5. The preparation method according to claim 3, characterized in that The adhesive is a polyurethane adhesive.

6. The preparation method according to claim 3, characterized in that The dispersant is sodium tripolyphosphate.

7. The preparation method according to claim 3, characterized in that The preservative is benzisothiazolinone.

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