Wet-process alkali-resistant one-time enamel glaze material and preparation method thereof

Abstract

The invention belongs to the technical field of glaze formulas, and discloses a wet-process alkali-resistant one-time enamel glaze and a preparation method thereof. The invention discloses a high-temperature-resistant ceramic coating which is prepared from the following compounds in percentage by mass: 20%-30% of SiO2, 15%-25% of ZrO, 10%-15% of Al2O3, 5%-10% of B2O3, 10%-15% of TiO2, 1%-5% of BaO, 6%-12% of K2O + Na2O, 3%-8% of CaF2 and 2%-3% of an adherence promoter. The glaze formula has the properties of good adherence, high temperature resistance, alkali corrosion resistance, simple enameling process, excellent porcelain surface quality and the like.

Description

Technical Field

[0001] The invention relates to the technical field of glaze formulation, and more particularly to a wet-process alkali-resistant one-time enamel and a preparation method thereof. Background Art

[0002] As the reserves of fossil energy continue to decline, clean energy such as wind energy, solar energy, and tidal energy are developing rapidly, but their shortcomings are particularly prominent, that is, they cannot provide stable power output. Therefore, energy storage technology plays a key role in the application of clean new energy. It can play the role of "peak shaving and valley flattening". At the same time, it is widely used in industrial waste heat recovery, flexible transformation of thermal power, heating and other fields, and shows great application potential in distributed energy integration.

[0003] Using alkaline molten salt for energy storage is a very common energy storage method at home and abroad. Under the guidance of national policies, China has increased its support for the research and development and industrialization of molten salt energy storage technology. Many companies and research institutions have actively participated in it and promoted the construction and implementation of a series of demonstration projects. Therefore, my country's molten salt energy storage industry has achieved rapid development. However, ordinary metal tanks cannot withstand the high-temperature corrosion of molten salts, and their surfaces need to be modified to resist alkali corrosion. The simplest way to modify is coating. Enamel, as a ceramic coating composite with metal, has good bonding with metal and can help metal resist acid and alkali corrosion and oxidation.

[0004] However, traditional enamel has many problems when facing alkaline corrosion from molten salt. The chemical stability of the enamel components of ordinary enamel is often insufficient under alkaline conditions. Generally speaking, when traditional enamel is in contact with alkaline solution for a long time, the alkali will react with certain components in the enamel, such as silicon dioxide, and destroy the structural integrity of the enamel. Therefore, improving the alkali corrosion resistance of the enamel layer is the key to realizing its application in the field of energy storage.

[0005] Therefore, developing a wet-process alkali-resistant one-time enamel material is a problem that those skilled in the art need to solve urgently. Summary of the invention

[0006] In view of the above problems, the present invention provides a wet-process alkali-resistant one-time enamel material and a production method thereof. The glaze material formula has the properties of good adhesion, high temperature resistance, alkali corrosion resistance, simple enameling process, and excellent porcelain surface quality.

[0007] One of the purposes of the present invention is to provide an enamel wet process alkali-resistant primary enamel material, which is composed of the following compounds in percentage by mass:

[0008] SiO2: 20% to 30%, ZrO: 15% to 25%, Al2O3: 10% to 15%, B2O3: 5% to 10%, TiO2: 10% to 15%, BaO: 1% to 5%, K2O+Na2O: 6% to 12%, CaF2: 3% to 8%, adhesive: 2% to 3%.

[0009] Preferably, the mass ratio of K2O to Na2O is 1:4.

[0010] Preferably, the adhesive is a combination of NiO, CoO, MnO2 and CuO, and the mass ratio of NiO, CoO, MnO2 and CuO is 5:2:1:2.

[0011] Further preferably, it is composed of the following compounds in percentage by mass:

[0012] SiO2: 23.5%, ZrO: 25%, Al2O3: 14.5%, B2O3: 7.3%, TiO2: 15%, BaO: 2.0%, K2O+Na2O: 6.6%, CaF2: 3.5%, adhesive (NiO, CoO, MnO2, CuO): 2.6%;

[0013] The mass ratio of K2O to Na2O is 1:4;

[0014] The adhesive is a combination of NiO, CoO, MnO2 and CuO, and the mass ratio of NiO, CoO, MnO2 and CuO is 5:2:1:2.

[0015] The second object of the present invention is to provide a method for preparing a primary enamel material, characterized in that it comprises the following steps:

[0016] (1) Mix the enamel materials according to the proportion;

[0017] (2) placing the mixture in a high temperature furnace and melting it at 1250-1350°C;

[0018] (3) After melting, put it into water and cool it rapidly to form a glaze frit;

[0019] (4) The glaze frit is turned into a ball mill and ground into a glaze.

[0020] SiO2 in glaze is one of the main components of glaze, providing a basic structural framework for glaze. It can form a three-dimensional network structure at high temperature, giving the glaze a certain shape and stability. The higher the amount of SiO2 in the glaze, the higher the firing temperature. Increasing the content of SiO2 within a certain range can improve the mechanical strength and hardness of the glaze, and can also improve the chemical stability and thermal stability of the glaze. At the same time, SiO2 has good chemical inertness and can resist the erosion of chemical substances such as acid, alkali, and salt. After adding silicon dioxide to the glaze, the resistance of the glaze to various chemical reagents can be enhanced.

[0021] ZrO in the glaze is a melting opacifier for the glaze, and can also be added to the ball mill as a grinding opacifier. It can also be used to improve the alkali resistance of the glaze. The increase in content will increase the hardness of the glaze surface and improve the wear resistance and alkali resistance of the glaze. In the invention formula, it can interact with silicon oxide, silicon oxide provides a place for zirconium oxide, and zirconium oxide can enhance the stability of the silicon oxide network.

[0022] B2O3 in the glaze is a solvent for the glaze and a network former for the glaze, which promotes the formation of a glass phase at low temperatures. The increase in the content of B2O3 will increase the mechanical strength of the glaze and improve its wear resistance. In the invention formula, the combination with ZrO can further improve the opacity and chemical corrosion resistance of the glaze. The presence of B2O3 helps to disperse zirconium oxide in the glaze, allowing it to play a better role. At the same time, it can reduce the melting point of aluminum oxide and promote the dissolution and dispersion of aluminum oxide in the glaze.

[0023] Al2O3 in the glaze is an intermediate oxide. Adding Al2O3 to the glaze can significantly improve the hardness and wear resistance of the glaze. At the same time, Al2O3 has good chemical inertness and can resist the erosion of chemical substances such as acids, alkalis, and salts. After adding alumina to the glaze, the chemical stability of the glaze can be improved. Al2O3 can also reduce the thermal expansion coefficient of the glaze, reduce its volume change when the temperature changes, and thus improve the thermal shock resistance of the porcelain. In the invention formula, it forms a strong network structure together with silicon oxide, which determines the physical and chemical properties of the glaze. The adjustment of the ratio of the two has an important influence on the melting temperature, viscosity, hardness, etc. of the glaze.

[0024] TiO2 in the glaze itself has good chemical stability, and can enhance the overall chemical stability of the glaze in the porcelain glaze. Especially in the face of acidic and alkaline environments, it can help resist acid and alkali erosion, reduce damage and discoloration caused by acid and alkali corrosion on the glaze surface, and thus maintain the appearance and performance of the porcelain glaze.

[0025] BaO in the glaze is a flux. An appropriate amount of barium oxide can improve the solubility of zirconium oxide and increase the alkali resistance and hardness of the glaze.

[0026] K2O and Na2O in the glaze are strong fluxing agents of the glaze, which can significantly reduce the melting temperature and high-temperature viscosity of the glaze, but have an adverse effect on the alkali resistance of the glaze. Reasonable dosage.

[0027] CaF2 in the glaze is a strong co-solvent that can reduce the high-temperature viscosity of the glaze during melting and also has a significant promoting effect on adhesion.

[0028] The adhesives in the glaze are NiO, CuO, CoO, and MnO2. They interact with the components in the glaze and can react with iron, allowing the glaze and the steel plate to penetrate each other, which is beneficial to the formation of a glaze adhesion layer. At the same time, they can affect the chemical stability of the glaze to a certain extent, and improve the acid and alkali resistance and wear resistance of the glaze to a certain extent.

[0029] The interaction of each component in the glaze provided by the present invention: silicon oxide (SiO2) as the main skeleton component of the glaze, together with aluminum oxide, forms the basic structure of the glaze, providing a basis for the attachment and reaction of other components. Combined with boron oxide, it can reduce the melting temperature and viscosity of the glaze, and improve the fluidity and uniformity of the glaze. Together with aluminum oxide, it forms a solid network structure to improve the strength and corrosion resistance of the glaze. Adjustment of the ratio of the two can change the performance of the glaze. For example, increasing the aluminum oxide content will make the glaze more resistant to high temperatures, but may cause the melting temperature of the glaze to increase. At the same time, the network structure of silicon oxide and aluminum oxide can accommodate a certain amount of zirconium oxide. The presence of zirconium oxide can improve the hardness, wear resistance and chemical stability of the glaze, and enhance the alkali resistance of the glaze.

[0030] Barium oxide, calcium fluoride, potassium oxide and sodium oxide can all react with silicon oxide to act as a dissolution aid.

[0031] It can be seen from the above technical scheme that compared with the prior art, the beneficial effects achieved by the present invention are as follows: through the overall ratio of the above components, the present invention makes the glaze as a whole have a good alkali resistance under the action of sufficient ZrO, and at the same time, through the interaction of NiO, CoO, MnO2, CuO and other components with the embryo, a good adhesion is produced, while keeping the porcelain surface smooth and flat. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Example 1

[0034] A wet alkali-resistant one-time enamel material, comprising the following components: ZrO, SiO2, B2O3, Al2O3, TiO2, BaO, Na2O, K2O, CaF2, and a sealant, wherein the mass ratio of K2O to Na2O is 1:4; the sealant is a combination of NiO, CoO, MnO2 and CuO, wherein the mass ratio of NiO, CoO, MnO2 and CuO is 5:2:1:2, and the specific mass fraction of each component is shown in Table 1; the glaze obtained in Example 1 is fired under the following three process conditions respectively:

[0035] 830℃, calcination 4.5min;

[0036] 850℃, sintering for 4.5min;

[0037] 870℃, sintering for 4.5min;

[0038] The enamel panels fired at different temperatures under the above process conditions were tested for porcelain layer thickness and visual inspection of porcelain surface quality. The main observation indicators were: the presence of pinholes and the severity of orange peel wrinkles. In addition, the glaze was tested for alkali resistance according to the detection method of GB9988-1988. The detailed data are recorded in Table 2.

[0039] Example 2

[0040] The main difference between this embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in Table 1; the test results of various items at different firing temperatures in this embodiment are detailed in Table 2.

[0041] Example 3

[0042] The main difference between this embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in Table 1; the test results of various items at different firing temperatures in this embodiment are detailed in Table 2.

[0043] Example 4

[0044] The main difference between this embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in Table 1; the test results of various items at different firing temperatures in this embodiment are detailed in Table 2.

[0045] Example 5

[0046] The main difference between this embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in Table 1; the test results of various items at different firing temperatures in this embodiment are detailed in Table 2.

[0047] Example 6

[0048] The main difference between this embodiment and embodiment 1 is that the mass fractions of the glaze components are different, and the specific differences are detailed in Table 1; the test results of various items at different firing temperatures in this embodiment are detailed in Table 2.

[0049] Control group

[0050] The inventor purchased common wet-process one-time enamel material from the market, the formula of which is as follows:

[0051] SiO2: 48.5%, B2O3: 13.0%, K2O+Na2O: 21.0%, Al2O3: 6.0%, CaF2: 7.2%, NiO: 1.2%, CaO: 0.8%, Fe2O3: 1.0%, MnO2: 0.4%, pigment: 0.9%

[0052] Firing under the following three process conditions:

[0053] 830℃, calcination 4.5min;

[0054] 850℃, sintering for 4.5min;

[0055] 870℃, calcination 4.5min;

[0056] The enamel panels fired at different temperatures under the above process conditions were tested for porcelain layer thickness and visual inspection of porcelain surface quality. The main observation indicators were: the presence of pinholes and the severity of orange peel wrinkles. In addition, the glaze was tested for alkali resistance according to the detection method of GB9988-1988. The detailed data are recorded in Table 2.

[0057] Table 1 List of mass fractions of components in Examples 1 to 6 (%)

[0058] Components Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 <![CDATA[SiO2]]> 23.5 30.0 30.0 23.5 30.0 23.5 ZrO 25.0 25.0 15.0 25.0 22.6 25.0 <![CDATA[Al2O3]]> 14.5 10.5 14.5 10.0 10.0 14.0 <![CDATA[B2O3]]> 7.3 7.3 7.3 7.3 7.3 7.3 <![CDATA[TiO2]]> 15.0 12.5 13.1 15.0 10.0 10.1 BaO 2.0 2.0 2.0 2.0 2.0 2.0 <![CDATA[Na2O+K2O]]> 6.6 6.6 12.0 11.1 12.0 12.0 <![CDATA[CaF2]]> 3.5 3.5 3.5 3.5 3.5 3.5 Adhesive agent 2.6 2.6 2.6 2.6 2.6 2.6

[0059] Table 2 Test results of Examples 1 to 6 and the control group under different process conditions

[0060]

[0061]

[0062] Combining Table 1 and Table 2, it can be seen that in Examples 1 to 6, when the mass percentages of the components are different and the firing processes are different, there are certain differences in the porcelain surface quality, adhesion, alkali resistance and other properties of the enamel plates; compared with the ordinary wet-process one-time enamel material of the control group, ZrO and TiO are added in the embodiments provided by the present invention, and the amount and ratio of the adhesion agent are changed, so that the glaze formula provided by the present invention has better adhesion and alkali resistance effects, among which Example 1 is the most preferred among all the formulas, and a good effect can be achieved when fired at 830°C and 4.5min.

[0063] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A wet-process alkali-resistant primary enamel material, characterized in that: It is composed of the following compounds in percentage by mass: SiO2: 20% to 30%, ZrO: 15% to 25%, Al2O3: 10% to 15%, B2O3: 5% to 10%, TiO2: 10% to 15%, BaO: 1% to 5%, K2O+Na2O: 6% to 12%, CaF2: 3% to 8%, adhesive: 2% to 3%.

2. The enamel wet process alkali-resistant primary enamel material according to claim 1, characterized in that: The mass ratio of K2O to Na2O is 1:

4.

3. The enamel wet process alkali-resistant primary enamel material according to claim 1, characterized in that: The adhesive is a combination of NiO, CoO, MnO2 and CuO, and the mass ratio of NiO, CoO, MnO2 and CuO is 5:2:1:

2.

4. The enamel wet process alkali-resistant primary enamel material according to claim 1, characterized in that: The following mass percentage of compounds composition: SiO2: 23.5%, ZrO: 25%, Al2O3: 14.5%, B2O3: 7.3%, TiO2: 15%, BaO: 2.0%, K2O+Na2O: 6.6%, CaF2: 3.5%, adhesive: 2.6%; The mass ratio of K2O to Na2O is 1:4; The adhesive is a combination of NiO, CoO, MnO2 and CuO, and the mass ratio of NiO, CoO, MnO2 and CuO is 5:2:1:

2.

5. A method for preparing a primary enamel material, characterized in that: The following steps are involved: (1) Mix the enamel material according to any one of claims 1 to 4 in proportion; (2) placing the mixture into a high temperature furnace to melt; (3) After melting, put it into water and cool it rapidly to form a glaze frit; (4) The glaze frit is turned into a ball mill and ground into a glaze.

6. The method for preparing a primary enamel material according to claim 5, characterized in that: The melting temperature in step (2) is 1250-1350°C.

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