A high-strength electric porcelain glaze and preparation method thereof

Abstract

The present invention discloses a high-strength electric porcelain glaze and a preparation method thereof, which belongs to the field of glaze technology. The high-strength electric porcelain glaze includes a basic electric porcelain glaze, a wear-resistant additive and a dispersant. The wear-resistant additive includes an aluminum oxide-yttrium oxide composite powder and graphene oxide; the addition amount of the dispersant is 0.1%-0.3% of the dry weight of the high-strength electric porcelain glaze; the addition amount of the wear-resistant additive is 4%-8% of the dry weight of the high-strength electric porcelain glaze. The present invention provides a high-strength electric porcelain glaze, which uses aluminum oxide-yttrium oxide composite powder and graphene oxide as wear-resistant additives to improve glaze performance. The aluminum oxide-yttrium oxide composite powder in the present invention can react with magnesium oxide and iron oxide (derived from ore raw materials such as potassium feldspar and kaolin) in the basic electric porcelain glaze to generate cordierite phase, thereby improving wear resistance. Graphene oxide can induce the precipitation of silicon dioxide, promote the generation of cordierite phase, and further improve wear resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of glazes, and in particular relates to a high-strength electric porcelain glaze and a preparation method thereof. Background Art

[0002] Insulators are a type of industrial ceramics, primarily insulating ceramics used in power industry systems. These include various line insulators and insulators for power station electrical equipment, as well as other insulating ceramics used to isolate or support live elements. Insulator glaze, the glaze layer on the surface of insulators, plays a decisive role in the ceramic's electrical insulation, chemical stability, and mechanical strength. However, in harsh, windy and sandy environments, the glaze is susceptible to wear. Once damaged, transmission losses increase dramatically, and even the risk of electrical leakage may occur.

[0003] In order to improve the wear resistance of electric porcelain glaze and prepare high-strength electric porcelain glaze, the wear resistance can be improved by adjusting the glaze formula or adding refractory substances. For example, the patent application with application number CN101844937A discloses a high-voltage electric porcelain glaze suitable for use in extremely cold areas and its preparation method. The particle size of zirconium silicate oxide or rare earth element oxide is controlled to be below 5μm and evenly distributed in the glaze, which is conducive to improving thermal stability and enhancing the surface hardness of the glaze. The application adopts the method of adjusting the glaze formula and increasing the content of refractory components. However, while improving the wear resistance, the application also requires increasing the firing temperature, increasing energy consumption and cost. In addition, the dispersion effect of zirconium silicate oxide or rare earth element oxide below 5μm is poor, which is easy to affect the overall performance of the glaze. Summary of the Invention

[0004] The object of the present invention is to provide a high-strength electric porcelain glaze and a preparation method thereof, so as to solve the problem of poor wear resistance of the electric porcelain glaze.

[0005] A high-strength electrical porcelain glaze, comprising a basic electrical porcelain glaze, a wear-resistant additive and a dispersant, wherein the wear-resistant additive comprises an aluminum oxide-yttrium oxide composite powder and graphene oxide;

[0006] The amount of the dispersant added is 0.1%-0.3% of the dry weight of the high-strength electrical porcelain glaze;

[0007] The added amount of the wear-resistant additive is 4%-8% of the dry weight of the high-strength electrical porcelain glaze.

[0008] Furthermore, the particle size of the wear-resistant additive is ≤5 μm.

[0009] Furthermore, the mass ratio of the aluminum oxide-yttrium oxide composite powder to the graphene oxide is 8:0.1.

[0010] Furthermore, the alumina-yttrium oxide composite powder is prepared by the following steps:

[0011] Alumina is added to a phosphoric acid solution and stirred. After solid-liquid separation and vacuum drying, it is added to deionized water, and polyacrylate ammonium dispersant is added for ultrasonic dispersion, followed by addition of yttrium nitrate. After stirring and dispersion, ammonia water is added to adjust the pH value of the system to 9, and stirring is continued. After the reaction is completed, the aluminum oxide-yttrium oxide composite powder is obtained by centrifugation, washing, drying, grinding and sieving.

[0012] Furthermore, the mass fraction of yttrium oxide in the alumina-yttrium oxide composite powder is 8%-10%.

[0013] Furthermore, the dispersant is prepared by the following steps:

[0014] Methyl acrylate and diethylenetriamine are used as raw materials and methanol is used as the reaction medium. Methyl acrylate is slowly added dropwise to a methanol solution of diethylenetriamine to cause a Michael addition reaction to generate a hyperbranched polyamide-amine. The molar ratio of methyl acrylate to diethylenetriamine is 1:1.1. The obtained hyperbranched polyamide-amine is mixed with methanol, ultrasonically dispersed, and then 3-glycidyloxypropyltrimethoxysilane is added and heated for reaction (heating at 80°C for 24 hours). After the reaction is completed, vacuum drying (temperature set at 40°C, vacuum degree of -0.09 MPa, drying) is performed to obtain a dispersant precursor. The molar ratio of the added amount of 3-glycidyloxypropyltrimethoxysilane to diethylenetriamine is 0.5:1.

[0015] The dispersant precursor was added to a formic acid aqueous solution and stirred at 60°C for 24 hours. Under acidic conditions, the -Si-O-CH3 (derived from 3-glycidoxypropyltrimethoxysilane) in the dispersant precursor hydrolyzed to -Si-OH. The macromolecular dispersant not only improved the dispersibility of materials such as graphene and alumina-yttrium oxide composite powders, but the -Si-OH formed after hydrolysis also had a fixing effect, improving the dispersion effect.

[0016] Furthermore, during the dropwise addition, the temperature was controlled within a range of 10-25°C. After the titration, the reaction temperature was set at 60°C for 1 hour, 100°C for 2 hours, and 120°C for 2 hours.

[0017] The concentration of the formic acid aqueous solution is 0.1 mol / L;

[0018] The usage ratio of the dispersant precursor and the formic acid aqueous solution is 1 g:20 mL.

[0019] Furthermore, the basic electrical porcelain glaze is any one of brown glaze and white glaze, or a combination of the two in any ratio.

[0020] A method for preparing high-strength electrical porcelain glaze comprises the following steps:

[0021] According to dry weight, electric porcelain glaze, wear-resistant additive and dispersant are mixed with water and ball milled to obtain a high-strength electric porcelain glaze.

[0022] Furthermore, after ball milling, the slurry is sieved through a 100-mesh sieve; after adding water, the slurry is allowed to stand to eliminate bubbles in the glaze slurry.

[0023] Beneficial effects of the present invention:

[0024] The present invention provides a high-strength electrical porcelain glaze comprising a base electrical porcelain glaze, a wear-resistant additive, and a dispersant. In the present invention, an aluminum oxide-yttrium oxide composite powder and graphene oxide are used as wear-resistant additives to improve glaze performance. The aluminum oxide-yttrium oxide composite powder reacts with magnesium oxide, iron oxide, and silicon dioxide (derived from mineral raw materials such as potassium feldspar, quartz, and kaolin) in the base electrical porcelain glaze to form a cordierite phase, thereby improving wear resistance. The graphene oxide can induce the precipitation of silicon dioxide, promoting the formation of the cordierite phase and further enhancing wear resistance.

[0025] The wear-resistant additive in the present invention is an alumina-yttrium oxide composite powder. Compared with the conventional mixture of alumina and yttrium oxide, the alumina in the present invention is first treated by chemical precipitation method and then added to the glaze. This not only facilitates the dispersion of the wear-resistant additive, but also is more conducive to the formation of a low eutectic phase during the sintering process, promotes diffusion and migration between substances, further promotes the densification of the sample, and improves the performance of the glaze.

[0026] In order to further improve the performance of the high-strength electrical porcelain glaze, the present invention adds a dispersant. The dispersant is prepared by reacting a hyperbranched polyamide-amine as a core with 3-glycidyloxypropyltrimethoxysilane. The dispersant has good dispersibility and can introduce silicon elements through the dispersant, thereby improving the performance of the glaze after sintering. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described 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 making any creative efforts shall fall within the scope of protection of the present invention.

[0028] The basic electrical porcelain glaze in this application includes the following raw materials by weight: 30 parts of potassium feldspar, 25 parts of quartz, 10 parts of kaolin, 15 parts of calcite, 20 parts of talc, and 5 parts of zirconium silicate. The composition of the raw materials is shown in Table 1 below:

[0029] Table 1

[0030] <![CDATA[SiO2]]> <![CDATA[Al2O3]]> <![CDATA[Fe2O3]]> CaO MgO <![CDATA[K2O]]> <![CDATA[Na2O]]> <![CDATA[ZrO2]]> IL Potassium feldspar 65.81 18.86 0.17 0.10 0.12 10.76 3.21 - 0.41 quartz 98.31 0.86 0.08 0.15 0.55 - - - 00.22 Kaolin 46.48 37.45 0.82 0.22 0.10 0.09 0.01 - 14.20 calcite 0.46 0.08 0.01 55.02 0.52 - 0.18 - 43.51 talc 61.89 3.01 0.35 0.47 33.22 - - - 0.13 Zirconium silicate 34.26 1.05 0.12 - - - - 64.14 0.25

[0031] Glazing: The base is glazed using the dipping method. The base is factory-molded for porcelain insulators and measures 100mm long x 100mm wide, with a thickness of 6mm to 10mm. The base is dried and cleaned before glazing. The firing temperature is 1250-1280°C in an oxidizing atmosphere.

[0032] Example 1

[0033] The preparation of the dispersant comprises the following steps:

[0034] Methyl acrylate was slowly added dropwise to a methanol solution of diethylenetriamine. During the addition process, the temperature range was controlled at 10-25°C. After the titration, the reaction temperature was set at 60°C for 1 hour, 100°C for 2 hours, and 120°C for 2 hours. The molar ratio of methyl acrylate to diethylenetriamine was 1:1.1. The obtained hyperbranched polyamide-amine was mixed with methanol, and after ultrasonic dispersion, 3-glycidyloxypropyltrimethoxysilane was added and reacted at 80°C for 24 hours. After the reaction was completed, the temperature was set to 40°C, the vacuum degree was -0.09 MPa, and the solution was dried to constant weight to obtain a dispersant precursor. The molar ratio of the added amount of 3-glycidyloxypropyltrimethoxysilane to diethylenetriamine was 0.5:1.

[0035] The dispersant precursor was added to a formic acid aqueous solution and stirred at 60°C for 24 hours. The concentration of the formic acid aqueous solution was 0.1 mol / L, and the ratio of the dispersant precursor to the formic acid aqueous solution was 1 g:20 mL.

[0036] Example 2

[0037] This embodiment provides a high-strength electrical porcelain glaze, including a basic electrical porcelain glaze, a wear-resistant additive, and a dispersant, wherein the wear-resistant additive includes an aluminum oxide-yttrium oxide composite powder and graphene oxide;

[0038] Alumina was added to a 1% by mass phosphoric acid solution and stirred for 30 minutes. After solid-liquid separation and vacuum drying at 70°C, it was added to deionized water, and polyacrylate ammonium dispersant was added for ultrasonic dispersion. Yttrium nitrate was added after stirring and dispersion. Ammonia water was added to adjust the pH value of the system to 9. Stirring was continued for 2 hours. After the reaction was completed, the aluminum oxide-yttrium oxide composite powder was obtained by centrifugation, washing, drying, grinding and sieving. The mass fraction of yttrium oxide in the aluminum oxide-yttrium oxide composite powder was 9%. The aluminum oxide-yttrium oxide composite powder was mixed with graphene oxide in a mass ratio of 8:0.1 to obtain a wear-resistant additive. The particle size of the wear-resistant additive was ≤5μm.

[0039] According to dry weight, the electric porcelain glaze, the wear-resistant additive and the dispersant prepared according to the proportion and method in Example 1 were mixed with water, and ball milled through a 100-mesh sieve. The amount of water was such that the density was in the range of 1.50±0.01g / cm3 After adding water, the mixture is allowed to stand for 20 minutes to eliminate bubbles in the glaze slurry to obtain a high-strength electric porcelain glaze. The amount of dispersant added is 0.2% of the dry weight of the high-strength electric porcelain glaze; the amount of wear-resistant additive added is 4% of the dry weight of the high-strength electric porcelain glaze.

[0040] Example 3

[0041] This embodiment provides a high-strength electrical porcelain glaze, including a basic electrical porcelain glaze, a wear-resistant additive, and a dispersant, wherein the wear-resistant additive includes an aluminum oxide-yttrium oxide composite powder and graphene oxide;

[0042] Alumina was added to a 1% by mass phosphoric acid solution and stirred for 30 minutes. After solid-liquid separation and vacuum drying at 70°C, it was added to deionized water, and polyacrylate ammonium dispersant was added for ultrasonic dispersion. Yttrium nitrate was added after stirring and dispersion. Ammonia water was added to adjust the pH value of the system to 9. Stirring was continued for 2 hours. After the reaction was completed, the aluminum oxide-yttrium oxide composite powder was obtained by centrifugation, washing, drying, grinding and sieving. The mass fraction of yttrium oxide in the aluminum oxide-yttrium oxide composite powder was 9%. The aluminum oxide-yttrium oxide composite powder was mixed with graphene oxide in a mass ratio of 8:0.1 to obtain a wear-resistant additive. The particle size of the wear-resistant additive was ≤5μm.

[0043] According to dry weight, the electric porcelain glaze, the wear-resistant additive and the dispersant prepared according to the proportion and method in Example 1 were mixed with water, and ball milled through a 100-mesh sieve. The amount of water was such that the density was in the range of 1.50±0.01g / cm 3 After adding water, the mixture is allowed to stand for 20 minutes to eliminate bubbles in the glaze slurry to obtain a high-strength electric porcelain glaze. The amount of the dispersant added is 0.2% of the dry weight of the high-strength electric porcelain glaze; the amount of the wear-resistant additive added is 5% of the dry weight of the high-strength electric porcelain glaze.

[0044] Example 4

[0045] This embodiment provides a high-strength electrical porcelain glaze, including a basic electrical porcelain glaze, a wear-resistant additive, and a dispersant, wherein the wear-resistant additive includes an aluminum oxide-yttrium oxide composite powder and graphene oxide;

[0046] Alumina was added to a 1% by mass phosphoric acid solution and stirred for 30 minutes. After solid-liquid separation and vacuum drying at 70°C, it was added to deionized water, and polyacrylate ammonium dispersant was added for ultrasonic dispersion. Yttrium nitrate was added after stirring and dispersion. Ammonia water was added to adjust the pH value of the system to 9. Stirring was continued for 2 hours. After the reaction was completed, the aluminum oxide-yttrium oxide composite powder was obtained by centrifugation, washing, drying, grinding and sieving. The mass fraction of yttrium oxide in the aluminum oxide-yttrium oxide composite powder was 9%. The aluminum oxide-yttrium oxide composite powder was mixed with graphene oxide in a mass ratio of 8:0.1 to obtain a wear-resistant additive. The particle size of the wear-resistant additive was ≤5μm.

[0047] According to dry weight, the electric porcelain glaze, the wear-resistant additive and the dispersant prepared according to the proportion and method in Example 1 were mixed with water, and ball milled through a 100-mesh sieve. The amount of water was such that the density was in the range of 1.50±0.01g / cm 3 After adding water, the mixture is allowed to stand for 20 minutes to eliminate bubbles in the glaze slurry to obtain a high-strength electric porcelain glaze. The amount of the dispersant added is 0.2% of the dry weight of the high-strength electric porcelain glaze; the amount of the wear-resistant additive added is 6% of the dry weight of the high-strength electric porcelain glaze.

[0048] Example 5

[0049] Compared with Example 2, the addition amount of the wear-resistant additive in this example is 7% of the dry weight of the high-strength electrical porcelain glaze, and the other raw materials and preparation process remain the same as those in Example 2.

[0050] Example 6

[0051] Compared with Example 2, the addition amount of the wear-resistant additive in this example is 8% of the dry weight of the high-strength electrical porcelain glaze, and the other raw materials and preparation process remain the same as those in Example 2.

[0052] Example 7

[0053] Compared with Example 5, the amount of dispersant added in this embodiment is 0.1% of the dry weight of the high-strength electrical porcelain glaze; the other raw materials and preparation process are the same as those in Example 4.

[0054] Example 8

[0055] Compared with Example 5, the amount of dispersant added in this embodiment is 0.3% of the dry weight of the high-strength electrical porcelain glaze; the other raw materials and preparation process are the same as those in Example 4.

[0056] Comparative Example 1

[0057] Compared with Example 2, this comparative example does not add the wear-resistant additive.

[0058] Comparative Example 2

[0059] Compared with Example 2, this comparative example replaces the wear-resistant additive with aluminum oxide, and the remaining raw materials and preparation process remain the same as those in Example 2.

[0060] Comparative Example 3

[0061] Compared with Example 2, this comparative example does not add a dispersant, and the remaining raw materials and preparation process remain the same as those in Example 2.

[0062] Comparative Example 4

[0063] Compared with Example 2, this comparative example is different from Example 2 in that the dispersant is replaced with sodium carboxymethyl cellulose, and the other raw materials and preparation process remain the same as those in Example 2.

[0064] Comparative Example 5

[0065] Compared with Example 2, this comparative example does not add graphene oxide, and the remaining raw materials and preparation process remain the same as those in Example 2.

[0066] Referring to the method described in GB / T 3810.7-2016, the rotation speed was adjusted to 600, and grinding was performed. The mass loss of each sample (a total of 5 samples) was measured, and the average wear value of Examples 2 to 8 and Comparative Example 1 was calculated. The results are shown in Table 2 below:

[0067] Table 2

[0068] project <![CDATA[Average wear amount (mg / cm 2 )]]> Example 2 13.5 Example 3 10.3 Example 4 9.2 Example 5 8.7 Example 6 8.5 Example 7 8.9 Example 8 8.9 Comparative Example 1 20.3 Comparative Example 2 18.5 Comparative Example 3 15.5 Comparative Example 4 14.8 Comparative Example 5 15.2

[0069] From the contents recorded in Table 2, it can be seen that with the increase in the amount of wear-resistant additives, the wear resistance is improved.

[0070] Example 9

[0071] Compared with Example 5, the mass fraction of yttrium oxide in the alumina-yttrium oxide composite powder in this example is 8%; the remaining raw materials and preparation process remain the same as those in Example 5.

[0072] Example 10

[0073] Compared with Example 5, the mass fraction of yttrium oxide in the alumina-yttrium oxide composite powder in this example is 10%; the remaining raw materials and preparation process remain the same as those in Example 5.

[0074] Comparative Example 6

[0075] Compared with Example 5, this comparative example replaces the wear-resistant additive with aluminum oxide and yttrium oxide, and the mass ratio of aluminum oxide to yttrium oxide is 100:9.

[0076] The flexural strength of the samples prepared in Example 5, Example 9, Example 10, and Comparative Example 6 was characterized using a WDW-50 material testing machine. The test method was 3-point flexure with a span of 50 mm. The results are shown in Table 3 below:

[0077] Table 3

[0078] project Flexural strength / N Example 5 10.6 Example 9 10.8 Example 10 10.4 Comparative Example 6 9.8

[0079] From the contents of Table 3, it can be seen that yttrium oxide in the alumina-yttrium oxide composite powder can promote mass transfer as a sintering aid. The alumina-yttrium oxide composite powder obtained after treatment is more conducive to the formation of a low eutectic phase during the sintering process, promotes grain growth and development, and improves the strength of the sample.

[0080] According to the test results, the high-strength electrical porcelain glaze prepared by the present invention has good wear resistance and flexural resistance.

[0081] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0082] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A high-strength electrical porcelain glaze, characterized in that: It includes basic electric porcelain glaze, wear-resistant additives and dispersants, wherein the wear-resistant additives include aluminum oxide-yttrium oxide composite powder and graphene oxide; The amount of the dispersant added is 0.1%-0.3% of the dry weight of the high-strength electrical porcelain glaze; The amount of the wear-resistant additive added is 4%-8% of the dry weight of the high-strength electrical porcelain glaze; The alumina-yttrium oxide composite powder is prepared by the following steps: Alumina is added to a phosphoric acid solution and stirred. After solid-liquid separation and vacuum drying, it is added to deionized water, ammonium polyacrylate is added, and yttrium nitrate is added after ultrasonic dispersion. After stirring and dispersion, ammonia water is added to adjust the pH value of the system to 9. Stirring is continued. After the reaction is completed, the aluminum oxide-yttrium oxide composite powder is obtained by centrifugation, washing, drying, grinding and sieving.

2. The high-strength electrical porcelain glaze according to claim 1, characterized in that: The particle size of the wear-resistant additive is ≤5 μm.

3. The high-strength electrical porcelain glaze according to claim 1, characterized in that: The mass ratio of the aluminum oxide-yttrium oxide composite powder to graphene oxide is 8:0.

1.

4. The high-strength electrical porcelain glaze according to claim 1, characterized in that: The mass fraction of yttrium oxide in the alumina-yttrium oxide composite powder is 8%-10%.

5. The high-strength electrical porcelain glaze according to claim 1, characterized in that: The dispersant is prepared by the following steps: Methyl acrylate and diethylenetriamine are used as raw materials and methanol is used as the reaction medium. Methyl acrylate is slowly added dropwise to a methanol solution of diethylenetriamine; the molar ratio of methyl acrylate to diethylenetriamine is 1:1.

1. The obtained hyperbranched polyamide-amine is mixed with methanol, ultrasonically dispersed, and then 3-glycidyloxypropyltrimethoxysilane is added and heated for reaction. After the reaction is completed, the mixture is vacuum dried to obtain a dispersant precursor; the molar ratio of the added amount of 3-glycidyloxypropyltrimethoxysilane to diethylenetriamine is 0.5:

1. The dispersant precursor was added to the formic acid aqueous solution and stirred for reaction at a temperature of 60°C.

6. The high-strength electrical porcelain glaze according to claim 5, characterized in that: During the addition process, the temperature was controlled in the range of 10-25°C. After the titration, the reaction temperature was set at 60°C for 1 hour, 100°C for 2 hours, and 120°C for 2 hours. The concentration of the formic acid aqueous solution is 0.1 mol / L; The usage ratio of the dispersant precursor and the formic acid aqueous solution is 1 g:20 mL.

7. The high-strength electrical porcelain glaze according to claim 1, characterized in that: The basic electric porcelain glaze is any one of brown glaze and white glaze, or a combination of the two in any proportion.

8. The method for preparing a high-strength electrical porcelain glaze according to claim 1, characterized in that: The steps include: According to dry weight, electric porcelain glaze, wear-resistant additive and dispersant are mixed with water and ball milled to obtain a high-strength electric porcelain glaze.

9. The method for preparing a high-strength electrical porcelain glaze according to claim 8, characterized in that: After ball milling, pass through a 100-mesh sieve; after adding water, let it stand to eliminate bubbles in the glaze slurry.