Glazes, glaze pastes and methods for high-temperature color development of atomic red ink

Abstract

This invention belongs to the field of ceramic inkjet technology and discloses a glaze, glaze slurry, and method for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink. The glaze formulation consists of: a base glaze, a high-calcium frit, fumed silica, and sodium aminoferrocyanide. The high-calcium frit in this formulation contains a large number of calcium ions, which increases the amount of calcium ions in the glaze during high-temperature molten states, thereby reducing the erosion of the tin-sphene structure of CaSnSiO5-Cr2O3 atomic red. Fumed silica also protects the CaSnSiO5-Cr2O3 atomic red color development to a certain extent on the glaze surface. Sodium aminoferrocyanide acts as a color developer, enhancing the color development of CaSnSiO5-Cr2O3 atomic red to a certain extent. The combined effect of these three components enables the CaSnSiO5-Cr2O3 atomic red ink to develop color even at high temperatures (1150-1250℃).

Description

Technical Field

[0001] This invention relates to the field of ceramic inkjet technology, specifically to a glaze, glaze slurry, and method for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink. Background Technology

[0002] With the advancement of ceramic inkjet technology, the decorative effects of ceramic tiles have become increasingly diverse. For Chinese people who love red-themed products, red signifies auspiciousness, celebration, and good fortune. As home decoration continues to evolve, low-temperature fired ceramic tiles are gradually being phased out by consumers, replaced by fully polished glazed ceramic tiles, antique-style ceramic tiles, and sintered stone ceramic tiles, which have lower water absorption rates and higher firing temperatures.

[0003] CaSnSiO5-Cr2O3 atomic red ink only develops color in low-temperature ceramic tiles in common glazes, and it barely develops in high-temperature polished glazes, antique tiles, and rock slabs. The main reason is that CaSnSiO5-Cr2O3 atomic red has a tin sphene structure, which is easily corroded and decomposed in high-temperature molten glazes, leading to structural damage and preventing it from producing its original pink color. Currently, the market uses encapsulated red ink as the main red color, but the encapsulating red material is zirconium silicate encapsulated with cadmium sulfide selenide, which contains the heavy metal cadmium, posing a certain health hazard.

[0004] CN107902890A describes a highly effective color-enhancing ultrafine silica material and its application; CN105000915A describes a color-enhancing agent for inkjet-printed ceramic tiles and its application method; CN 105906336A describes a method for making ferric ions appear red inside ceramic tiles. These inventions utilize the principle that ultrafine silica materials can enable ions to penetrate the ceramic body and produce color, and are mainly applied to inkjet printing systems. Since conventional CaSnSiO5-Cr2O3 atomic red ink is only printed on the glaze surface, simply adding ultrafine silica materials cannot enable CaSnSiO5-Cr2O3 atomic red to produce color at high temperatures (1150-1250℃).

[0005] Therefore, if a glaze can be prepared that allows CaSnSiO5-Cr2O3 atomic red to exhibit color at high temperatures, it can replace red pigments coated with heavy metals, thus making it more beneficial for ceramic applications. Summary of the Invention

[0006] The purpose of this invention is to overcome at least one deficiency of the prior art and to provide a glaze, glaze paste and method for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink.

[0007] The technical solution adopted in this invention is:

[0008] In the first aspect, the present invention provides a glaze for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink, wherein the glaze is formulated as follows: base glaze, high-calcium frit, fumed silica, sodium aminoferrocyanide, and the content of CaO in the high-calcium frit is not less than 15%.

[0009] In some instances, the amount of the high-calcium frit used is 2 to 10% of the mass of the base glaze.

[0010] In some instances, the amount of fumed silica used is 0.1 to 6% of the mass of the base glaze.

[0011] In some instances, the amount of sodium aminoferrocyanide used is 0.1 to 5% of the mass of the base glaze.

[0012] In some examples, the raw material composition of the base glaze is as follows: 2-30% sodium feldspar, 10-20% potassium feldspar, 0-20% air-knife clay, 0-10% ball clay, 0-10% calcined talc, 0-15% calcined clay, 0-15% barium carbonate, 0-9% zinc oxide, 5-30% quartz, 1-10% alumina, and 0-20% zirconium silicate; or the chemical composition of the base glaze is as follows: 50-60% SiO2, 30-35% Al2O3, 0-5% CaO, 0-3% MgO, 2-5% K2O, 3-6% Na2O, and 1-20% ZrO2.

[0013] In some instances, the high-calcium frit is composed of the following components by mass ratio: SiO2 40-60%, Al2O3 20-30%, CaO 20-50%, MgO 5-10%, K2O 0-5%, and Na2O 0-6%.

[0014] In some instances, the specific surface area of ​​the fumed silica is greater than 10 m². 2 / g.

[0015] Secondly, the present invention provides a glaze slurry, the composition of which is as described in the first aspect, and its preparation method includes the following steps:

[0016] 1) The base glaze and high-calcium frit are mixed in a certain proportion to obtain a dry powder, and then water is added for ball milling to obtain a glaze slurry;

[0017] 2) The glaze slurry is sieved, and then fumed silica and sodium ferrocyanide solution are added, ball-milled and mixed, and then sieved again. The viscosity and density are adjusted to obtain the glaze material that enables CaSnSiO5-Cr2O3 atomic red ink to develop color at high temperature.

[0018] In some instances, the glaze slurry also contains appropriate amounts of descaling agent and / or viscosity modifier.

[0019] Thirdly, the present invention provides a method for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink, comprising the following steps:

[0020] S1) Prepare the glaze described in the first aspect into a glaze slurry;

[0021] S2) Apply the glaze slurry onto the ceramic tile body;

[0022] S3) Apply CaSnSiO5-Cr2O3 atomic red ink to the glaze layer, and fire it at 1150-1250℃ after drying.

[0023] The beneficial effects of this invention are:

[0024] The glaze of this invention contains a high concentration of calcium ions in its high-calcium frit, which increases the amount of calcium ions in the glaze during its high-temperature molten state, thereby reducing the erosion of the CaSnSiO5-Cr2O3 atomic red tin sphene structure. Fumed silica also provides some protection for the CaSnSiO5-Cr2O3 atomic red color development on the glaze surface. Sodium ferrocyanide, as a color developer, enhances the color development of CaSnSiO5-Cr2O3 atomic red to a certain extent. Combining these factors, the invention achieves the effect of enabling CaSnSiO5-Cr2O3 atomic red ink to develop color even at high temperatures (1150-1250℃). Detailed Implementation

[0025] In the first aspect, the present invention provides a glaze for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink, wherein the glaze is formulated as follows: base glaze, high-calcium frit, fumed silica, sodium aminoferrocyanide, and the content of CaO in the high-calcium frit is not less than 15%.

[0026] The amount of high-calcium frit can be adjusted according to the amount of CaSnSiO5-Cr2O3 atomic red ink to ensure the high-temperature color development effect of CaSnSiO5-Cr2O3 atomic red ink. In some examples, the amount of high-calcium frit is 2 to 10% of the mass of the base glaze.

[0027] In some instances, the amount of fumed silica used is 0.1 to 6% of the mass of the base glaze.

[0028] In some instances, the amount of sodium aminoferrocyanide used is 0.1 to 5% of the mass of the base glaze.

[0029] The base glaze components are conventionally selected, and their main function is to form the main body of the glaze layer. In some examples, the raw material composition of the base glaze is as follows: sodium feldspar 2-30%, potassium feldspar 10-20%, air-knife clay 0-20%, ball clay 0-10%, calcined talc 0-10%, calcined clay 0-15%, barium carbonate 0-15%, zinc oxide 0-9%, quartz 5-30%, alumina 1-10%, zirconium silicate 0-20%; or the chemical composition of the base glaze is as follows: SiO2 50-60%, Al2O3 30-35%, CaO 0-5%, MgO 0-3%, K2O 2-5%, Na2O 3-6%, ZrO2 1-20%.

[0030] High-calcium frit, due to its higher calcium ion content, results in a greater concentration of calcium ions in the molten glaze at high temperatures, thereby reducing erosion of the CaSnSiO5-Cr2O3 atomic red tin sphene structure. In some examples, the composition of the high-calcium frit, by mass ratio, is: SiO2 40–60%, Al2O3 20–30%, CaO 20–50%, MgO 5–10%, K2O 0–5%, and Na2O 0–6%. This composition of high-calcium frit can better reduce erosion of the CaSnSiO5-Cr2O3 atomic red tin sphene structure.

[0031] In some instances, the specific surface area of ​​the fumed silica is greater than 10 m². 2 / g. Fumed silica has a large specific surface area, which can protect the CaSnSiO5-Cr2O3 atomic red color on the surface of the glaze.

[0032] Secondly, the present invention provides a glaze slurry, the composition of which is as described in the first aspect, and its preparation method includes the following steps:

[0033] 1) The base glaze and high-calcium frit are mixed in a certain proportion to obtain a dry powder, and then water is added for ball milling to obtain a glaze slurry;

[0034] 2) The glaze slurry is sieved, and then fumed silica and sodium ferrocyanide solution are added, ball-milled and mixed, and then sieved again. The viscosity and density are adjusted to obtain the glaze material that enables CaSnSiO5-Cr2O3 atomic red ink to develop color at high temperature.

[0035] In some instances, the glaze slurry also contains appropriate amounts of descaling agent and / or viscosity modifier.

[0036] Thirdly, the present invention provides a method for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink, comprising the following steps:

[0037] S1) Prepare the glaze described in the first aspect into a glaze slurry;

[0038] S2) Apply the glaze to the ceramic tile body;

[0039] S3) Apply CaSnSiO5-Cr2O3 atomic red ink to the glaze layer, dry it, and then fire it at 1150-1250℃.

[0040] The following disclosure provides many different implementations or examples for different ways of implementing the present invention.

[0041] For ease of comparison, the following examples use the following raw material composition of the base glaze: 6.6% sodium feldspar, 25% potassium feldspar, 16.6% air-knife clay, 4% ball clay, 8.2% calcined talc, 5% calcined clay, 2.8% barium carbonate, 0.8% zinc oxide, 19% quartz, 2% alumina, and 10% zirconium silicate.

[0042] The high-calcium frit used in the following examples has the following composition by mass: SiO2 44%, Al2O3 20%, CaO 27%, MgO 7%, K2O 1.5%, Na2O 0.5%.

[0043] The glazes and corresponding ceramic tile preparation methods of each embodiment and comparative example include the following steps:

[0044] S1) Mix the first part of the base glaze and the second part of the high-calcium frit in a certain proportion, then add appropriate proportions of water, sodium tripolyphosphate and sodium carboxymethyl cellulose, and ball mill for 4-7 minutes to achieve a certain fineness.

[0045] S2) Sieve the glaze slurry from the previous ball milling step through a 120-mesh sieve;

[0046] S3) Put the sieved glaze slurry obtained in the previous step back into the ball mill jar, and add a certain proportion of fumed silica and sodium aminoferrocyanide solution, and quickly ball mill to mix for 1-10 seconds.

[0047] S4) The glaze slurry obtained in the previous step is sieved through a 120-mesh sieve to obtain a glaze slurry that improves the color development of CaSnSiO5-Cr2O3 atomic red ink.

[0048] S5) Apply the glaze obtained in the previous step to the ceramic tile body by pouring or spraying glaze.

[0049] S6) Print or screen print pink ink on the tile obtained in the previous step, and then fire it at 1150-1250℃.

[0050] The amounts of base glaze, high-calcium frit, water, sodium tripolyphosphate, sodium carboxymethyl cellulose, fumed silica, and sodium aminoferrocyanide solution used in each embodiment and comparative example are shown in Table 1 below.

[0051] Table 1. Composition of glazes in different examples

[0052] Unit / g S1 S2 S3 S4 D1 D2 D3 D4 base glaze 100 100 100 100 100 100 100 100 High-calcium frit 5 4 4 3 0 0 0 4 Fumed silica 3 3 4 5 0 0 0 3 Precipitated silica 0 0 0 0 0 3 5 0 Sodium aminoferrocyanide 1 2 1 1 0 0 0 0 Potassium ferrocyanide 0 0 0 0 0 0 0 2 water 47 46 47 47 48 48 48 46 Sodium tripolyphosphate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Sodium carboxymethyl cellulose 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15

[0053] Note: In the table, S represents an example and D represents a comparative example. For example, S1 represents Example 1 and D1 represents Comparative Example 1.

[0054] Lab value is an important color control and management indicator in a color system. The L value represents the brightness of an object, ranging from black to white; the a value represents the red-green hue of an object, with positive values ​​indicating red and negative values ​​indicating green; the b value represents the yellow-blue hue of an object, with positive values ​​indicating yellow and negative values ​​indicating blue. The Lab value results are shown in Table 2, comparing data from Examples 1, 2, 3, and Comparative Example 1.

[0055] Table 2. Color detection results for different examples

[0056] Sample number L a b Example 1 70.98 7.98 1.41 Example 2 70.84 7.86 1.43 Example 3 70.41 7.69 1.38 Example 4 70.66 7.78 1.52 Comparative Example 1 74.64 1.15 -0.40 Comparative Example 2 74.55 1.12 -0.41 Comparative Example 3 75.20 1.14 -0.42 Comparative Example 4 75.77 1.16 -0.40

[0057] As can be seen from the Lab values ​​in the data table above, Examples 1 to 4 can significantly improve the color development of CaSnSiO5-Cr2O3 atomic red ink at 1150℃. However, the comparative example, due to the absence of high-calcium frit, fumed silica, and sodium ferrocyanide, showed very poor atomic red color development, with virtually no color development.

[0058] The above is a further detailed description of the present invention and should not be considered as a limitation on the specific implementation of the present invention. For those skilled in the art, simple deductions or substitutions without departing from the concept of the present invention are all within the protection scope of the present invention.

Claims

1. A glaze for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink, characterized in that, The glaze formulation consists of: a base glaze, a high-calcium frit, fumed silica, and sodium aminoferrocyanide. The high-calcium frit contains no less than 15% CaO. The amount of the high-calcium frit used is 2-10% of the mass of the base glaze. The amount of fumed silica used is 0.1-6% of the mass of the base glaze. The amount of sodium aminoferrocyanide used is 0.1-5% of the mass of the base glaze. The components of the high-calcium frit are in the following mass ratio: SiO2 40-60%, Al2O3 20-30%, CaO 20-50%, MgO 5-10%, K2O 0-5%, and Na2O 0-6%. The sum of the mass ratios of the components of the high-calcium frit is 100%.

2. The glaze according to claim 1, characterized in that, The raw material composition of the base glaze is as follows: sodium feldspar 2-30%, potassium feldspar 10-20%, air-knife clay 0-20%, ball clay 0-10%, calcined talc 0-10%, calcined clay 0-15%, barium carbonate 0-15%, zinc oxide 0-9%, quartz 5-30%, alumina 1-10%, zirconium silicate 0-20%; or the chemical composition of the base glaze is as follows: SiO2 50-60%, Al2O3 30-35%, CaO 0-5%, MgO 0-3%, K2O 2-5%, Na2O 3-6%, ZrO2 1-20%, and the sum of the chemical composition of the base glaze is 100%.

3. The glaze according to claim 1 or 2, characterized in that, The specific surface area of ​​the fumed silica is greater than 10 m². 2 / g.

4. A glaze paste, characterized in that, Its glaze composition is as described in any one of claims 1 to 3, and its preparation method includes the following steps: 1) The base glaze and high-calcium frit are mixed in a certain proportion to obtain a dry powder, and then water is added for ball milling to obtain a glaze slurry; 2) The glaze slurry is sieved, and then fumed silica and sodium ferrocyanide solution are added, ball-milled and mixed, and then sieved again. The viscosity and density are adjusted to obtain the glaze material that enables CaSnSiO5-Cr2O3 atomic red ink to develop color at high temperature.

5. The glaze paste according to claim 4, characterized in that, It also contains a suitable amount of desiccant and / or viscosity modifier.

6. A method for high-temperature color development of CaSnSiO5-Cr2O3 atomic red ink, comprising the following steps: The glaze according to any one of claims 1 to 3 is made into a glaze slurry; Apply the glaze to the ceramic tile body; CaSnSiO5-Cr2O3 atomic red ink is applied to the glaze layer, and after drying, it is fired at 1150-1250℃.