Anti-pollution flashover ceramic insulator and preparation method thereof

Abstract

The invention relates to the field of insulators, in particular to an anti-pollution flashover ceramic insulator and a preparation method thereof. The glaze layer is prepared from the following raw materials in parts by weight: 40-50 parts of potassium feldspar, 10-15 parts of Suzhou clay, 10-15 parts of calcite, 15-20 parts of quartz, 1-5 parts of aluminum oxide, 1-5 parts of magnesium oxide and 5-10 parts of modified halloysite nanotubes; the ceramic insulator is characterized in that a modified halloysite nanotube is loaded with a dialkyl dithiocarbamic acid metal salt-amino triazine copolymer, the glaze layer is the key for long-term use of the ceramic insulator in a severe environment, and the ceramic insulator is endowed with certain antifouling performance and photocatalytic performance, so that the service life of the insulator is prolonged, the service life of the ceramic insulator is prolonged, and the service life of the ceramic insulator is prolonged. The safe and stable operation of the power transmission line is ensured, and the maintenance cost of line operation is reduced.

Description

Technical Field

[0001] The present invention relates to the field of insulators, and particularly to an anti-fouling flashover ceramic insulator and a preparation method thereof. Background Art

[0002] In power transmission and distribution systems, insulators, as key components for supporting conductors and isolating electric currents, undertake the core task of ensuring the safe operation of the power grid. Their performance directly affects the reliability, stability, and anti-environmental interference ability of transmission lines. However, under the dual action of complex natural conditions (such as haze, salt fog, industrial pollutants) and electrical stress, dirt is likely to accumulate on the surface of insulators, leading to the phenomenon of fouling flashover and causing large-scale power outages. How to improve the anti-fouling flashover performance of insulators is of great significance for ensuring the safe and stable operation of transmission lines and reducing the maintenance cost of line operation. Summary of the Invention

[0003] Object of the Invention: Aiming at the above technical problems, the present invention provides an anti-fouling flashover ceramic insulator and a preparation method thereof.

[0004] The technical solution adopted is as follows:

[0005] An anti-fouling flashover ceramic insulator is composed of a ceramic matrix and a glaze layer;

[0006] By weight, the glaze layer is prepared from the following raw materials:

[0007] 40 - 50 parts of potassium feldspar, 10 - 15 parts of Suzhou clay, 10 - 15 parts of calcite, 15 - 20 parts of quartz, 1 - 5 parts of alumina, 1 - 5 parts of magnesia, 5 - 10 parts of modified halloysite nanotubes;

[0008] The modified halloysite nanotubes are loaded with a metal dihydrocarbyldithiocarbamate - aminotriazine copolymer.

[0009] Further, the metal dihydrocarbyldithiocarbamate is zinc dihydrocarbyldithiocarbamate and / or antimony dihydrocarbyldithiocarbamate.

[0010] Further, the structural formula of the metal dihydrocarbyldithiocarbamate is as follows:

[0011]

[0012] R1 and R2 are the same or different, and each independently is an alkenyl group, M is Zn or Sb, and n is 2, 3, or 4.

[0013] Further, R1 and R2 are the same.

[0014] Further, M is preferably Sb;

[0015] Further, n is preferably 3;

[0016] Further, R1 and R2 are C2-C6 alkenyl groups.

[0017] Furthermore, R1 and R2 are preferably allyl groups.

[0018] Furthermore, the metal dialkyldithiocarbamate is preferably antimony diallyldithiocarbamate, and its structural formula is as follows:

[0019]

[0020] Further, the preparation route of the antimony diallyldithiocarbamate is as follows:

[0021]

[0022] Further, the amino triazine is 2-vinyl-4,6-diamino-1,3,5-triazine and / or 2-allyl-4,6-diamino-1,3,5-triazine.

[0023] Further, the amino triazine is preferably 2-vinyl-4,6-diamino-1,3,5-triazine.

[0024] Further, the preparation method of the modified halloysite nanotubes is as follows:

[0025] Disperse the halloysite nanotubes in ethanol, then add ammonia water and deionized water. After stirring evenly, add 3-(methacryloyloxy)propyltrimethoxysilane for reaction. After the reaction is completed, collect the precipitate and dry it to obtain functionalized halloysite nanotubes. Disperse the functionalized halloysite nanotubes in an organic solvent, then add the metal dialkyldithiocarbamate, amino triazine and free radical initiator, stir and react, collect the product, wash it, and dry it.

[0026] Further, the mass ratio of the functionalized halloysite nanotubes, metal dialkyldithiocarbamate and amino triazine is 1:0.1-1:0.1-1, and the mass ratio of the functionalized halloysite nanotubes, metal dialkyldithiocarbamate and amino triazine is preferably 1:0.5:0.2.

[0027] Further, the ceramic matrix is made of alumina.

[0028] The present invention also provides a preparation method of an anti-fouling flashover ceramic insulator:

[0029] Mix potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water and ball-mill them to obtain a glaze. Apply the glaze on a ceramic substrate to obtain a green body. Dry the green body and then put it into a muffle furnace. First, heat it to 600 - 800 °C and keep it warm for 1 - 2 h, and then heat it to 1100 - 1200 °C and sinter it for 1 - 5 h.

[0030] It has the following beneficial effects:

[0031] The present invention provides an anti - pollution - flash ceramic insulator. The addition of halloysite nanotubes in the glaze layer can form a micro - nano composite rough surface. This rough surface increases the contact angle by increasing the discontinuity of the gas - liquid - solid three - phase contact line, improves the hydrophobicity of the glaze surface, and endows it with good waterproof, oil - proof and anti - pollution effects.

[0032] The present invention further loads a metal dithiocarbamate - aminotriazine copolymer on the halloysite nanotubes. When sintering, the metal dithiocarbamate decomposes to obtain metal sulfide, and aminotriazine undergoes a high - temperature pyrolysis reaction to obtain g - C3N4. At the same time, a small part of S element is incorporated into g - C3N, which expands the visible - light absorption range of g - C3N4 and narrows its band gap, thereby improving its photocatalytic performance. The metal sulfide can also be complementary to the energy band structure of g - C3N4 to form a heterojunction, promoting the efficient separation of photo - generated carriers. Through energy - band matching, charge - separation optimization, light - absorption range expansion and heterojunction - interface optimization, the two jointly improve the photocatalytic performance of the glaze layer and achieve the efficient degradation of pollutants.

[0033] In the present invention, the glaze layer is the key for the ceramic insulator to maintain long - term use in a harsh environment. It endows the ceramic insulator with certain anti - pollution performance and photocatalytic performance, enabling it to decompose the organic matter contaminated on the surface through photocatalysis, thereby achieving the purpose of degrading dirt, preventing flashover phenomena, increasing the service life of the insulator, ensuring the safe and stable operation of the transmission line, and reducing the maintenance cost of line operation. Specific embodiments

[0034] For those not specifying specific conditions in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase. Technologies not mentioned in the present invention refer to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel tests and adopt the same treatment steps and parameters.

[0035] Example 1:

[0036] An anti - pollution - flash ceramic insulator is composed of an alumina ceramic substrate and a glaze layer;

[0037] By weight, the glaze layer is prepared from the following raw materials:

[0038] 45 parts of potassium feldspar, 12 parts of Suzhou clay, 10 parts of calcite, 18 parts of quartz, 3 parts of alumina, 2 parts of magnesia, 5 parts of modified halloysite nanotubes;

[0039] The preparation method of the modified halloysite nanotubes is as follows:

[0040] Add 2.92 g of antimony trioxide and 100 ml of absolute ethanol into a flask. After stirring evenly, add 5.85 g of diallylamine under ice bath conditions. Continue stirring for 0.5 h, then dropwise add 4.57 g of carbon disulfide. After the addition is complete, continue the reaction for 1 h, then remove the ice bath and continue the reaction for 1 h under the water bath conditions of 45 - 50 °C. Finally, filter and collect the yellow precipitate formed by the reaction, wash it with absolute ethanol and dry it to obtain antimony diallyldithiocarbamate. Disperse 10 g of halloysite nanotubes in 1000 ml of ethanol, then add 150 ml of ammonia water and 100 ml of deionized water. Stir for 24 h, then add 10 ml of 3-(methacryloyloxy)propyltrimethoxysilane and continue stirring and reacting for 48 h. After the reaction is completed, centrifuge to collect the precipitate and dry it to obtain functionalized halloysite nanotubes. Disperse 10 g of functionalized halloysite nanotubes in 200 ml of xylene, then add 5 g of antimony diallyldithiocarbamate, 2 g of 2-vinyl-4,6-diamino-1,3,5-triazine and 0.01 g of free radical initiator AIBN. Stir and react under the water bath conditions of 60 °C for 5 h, then filter, collect the product, wash it with absolute ethanol and dry it.

[0041] The preparation method of the above anti-fouling flashover ceramic insulator:

[0042] Add potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water into a ball milling tank, and mix and ball mill on a planetary ball mill for 10 h to obtain glaze. Apply the glaze on the alumina ceramic substrate to obtain a green body, with the coating thickness of 10 ± 1 μm. After drying the green body, put it into a muffle furnace, first heat it to 700 °C at a rate of 1 °C / min and keep it warm for 1.5 h, then heat it to 1200 °C at a rate of 5 °C / min and sinter for 2 h.

[0043] Example 2:

[0044] An anti-fouling flashover ceramic insulator, which consists of an alumina ceramic substrate and a glaze layer;

[0045] By weight, the glaze layer is prepared from the following raw materials:

[0046] 45 parts of potassium feldspar, 12 parts of Suzhou clay, 10 parts of calcite, 18 parts of quartz, 3 parts of alumina, 2 parts of magnesia, 6 parts of modified halloysite nanotubes;

[0047] The preparation method of the modified halloysite nanotubes is the same as that in Example 1;

[0048] The preparation method of the above anti-fouling flashover ceramic insulator:

[0049] Add potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water into a ball milling tank, mix and ball mill on a planetary ball mill for 10 h to obtain a glaze. Apply the glaze on an alumina ceramic substrate to obtain a green body, with a coating thickness of 10 ± 1 μm. After drying the green body, put it into a muffle furnace and first heat it to 700 °C at a rate of 1 °C / min and hold for 1.5 h, then heat it to 1200 °C at a rate of 5 °C / min and sinter for 2 h.

[0050] Example 3:

[0051] An anti-fouling flashover ceramic insulator is composed of an alumina ceramic substrate and a glaze layer;

[0052] By weight, the glaze layer is prepared from the following raw materials:

[0053] 45 parts of potassium feldspar, 12 parts of Suzhou clay, 10 parts of calcite, 18 parts of quartz, 3 parts of alumina, 2 parts of magnesia, 7 parts of modified halloysite nanotubes;

[0054] The preparation method of the modified halloysite nanotubes is the same as that in Example 1;

[0055] The preparation method of the above anti-fouling flashover ceramic insulator:

[0056] Add potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water into a ball milling tank, mix and ball mill on a planetary ball mill for 10 h to obtain a glaze. Apply the glaze on an alumina ceramic substrate to obtain a green body, with a coating thickness of 10 ± 1 μm. After drying the green body, put it into a muffle furnace and first heat it to 700 °C at a rate of 1 °C / min and hold for 1.5 h, then heat it to 1200 °C at a rate of 5 °C / min and sinter for 2 h.

[0057] Example 4:

[0058] An anti-fouling flashover ceramic insulator is composed of an alumina ceramic substrate and a glaze layer;

[0059] By weight, the glaze layer is prepared from the following raw materials:

[0060] 45 parts of potassium feldspar, 12 parts of Suzhou clay, 10 parts of calcite, 18 parts of quartz, 3 parts of alumina, 2 parts of magnesia, 8 parts of modified halloysite nanotubes;

[0061] The preparation method of the modified halloysite nanotubes is the same as that in Example 1;

[0062] The preparation method of the above anti-fouling flashover ceramic insulator:

[0063] Potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water were added to a ball milling tank and mixed and ball milled on a planetary ball mill for 10 h to obtain a glaze. The glaze was applied to an alumina ceramic substrate to obtain a green body with a coating thickness of 10 ± 1 μm. After drying the green body, it was placed in a muffle furnace and first heated to 700 °C at a rate of 1 °C / min and held for 1.5 h, and then heated to 1200 °C at a rate of 5 °C / min and sintered for 2 h.

[0064] Example 5:

[0065] An anti-fouling flashover ceramic insulator consists of an alumina ceramic substrate and a glaze layer;

[0066] By weight, the glaze layer is prepared from the following raw materials:

[0067] 45 parts of potassium feldspar, 12 parts of Suzhou clay, 10 parts of calcite, 18 parts of quartz, 3 parts of alumina, 2 parts of magnesia, 9 parts of modified halloysite nanotubes;

[0068] The preparation method of the modified halloysite nanotubes is the same as that in Example 1;

[0069] The preparation method of the above anti-fouling flashover ceramic insulator:

[0070] Potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water were added to a ball milling tank and mixed and ball milled on a planetary ball mill for 10 h to obtain a glaze. The glaze was applied to an alumina ceramic substrate to obtain a green body with a coating thickness of 10 ± 1 μm. After drying the green body, it was placed in a muffle furnace and first heated to 700 °C at a rate of 1 °C / min and held for 1.5 h, and then heated to 1200 °C at a rate of 5 °C / min and sintered for 2 h.

[0071] Example 6:

[0072] An anti-fouling flashover ceramic insulator consists of an alumina ceramic substrate and a glaze layer;

[0073] By weight, the glaze layer is prepared from the following raw materials:

[0074] 45 parts of potassium feldspar, 12 parts of Suzhou clay, 10 parts of calcite, 18 parts of quartz, 3 parts of alumina, 2 parts of magnesia, 10 parts of modified halloysite nanotubes;

[0075] The preparation method of the modified halloysite nanotubes is the same as that in Example 1;

[0076] The preparation method of the above anti-fouling flashover ceramic insulator:

[0077] Potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water were added to a ball milling jar and mixed and ball milled on a planetary ball mill for 10 h to obtain a glaze. The glaze was applied to an alumina ceramic substrate to obtain a green body with a coating thickness of 10 ± 1 μm. After drying the green body, it was placed in a muffle furnace and first heated to 700 °C at a rate of 1 °C / min and held for 1.5 h, and then heated to 1200 °C at a rate of 5 °C / min and sintered for 2 h.

[0078] Comparative Example 1:

[0079] It was basically the same as Example 1, except that modified halloysite nanotubes were not added.

[0080] Comparative Example 2:

[0081] It was basically the same as Example 1, except that antimony diallyldithiocarbamate was not added during the preparation of the modified halloysite nanotubes.

[0082] The preparation method of the modified halloysite nanotubes is as follows:

[0083] 10 g of halloysite nanotubes were dispersed in 1000 ml of ethanol, then 150 ml of ammonia water and 100 ml of deionized water were added. After stirring for 24 h, 10 ml of 3-(methacryloyloxy)propyltrimethoxysilane was added, and the stirring reaction was continued for 48 h. After the reaction, the precipitate was collected by centrifugation and dried to obtain functionalized halloysite nanotubes. 10 g of functionalized halloysite nanotubes were dispersed in 200 ml of xylene, then 2 g of 2-vinyl-4,6-diamino-1,3,5-triazine and 0.01 g of free radical initiator AIBN were added. After stirring and reacting at 60 °C in a water bath for 5 h, filtration was carried out, the product was collected, washed with absolute ethanol and dried.

[0084] Comparative Example 3:

[0085] It was basically the same as Example 1, except that 2-vinyl-4,6-diamino-1,3,5-triazine was not added during the preparation of the modified halloysite nanotubes.

[0086] The preparation method of the modified halloysite nanotubes is as follows:

[0087] Add 2.92 g of antimony trioxide and 100 ml of absolute ethanol into a flask. After stirring evenly, add 5.85 g of diallylamine under ice bath conditions. Continue stirring for 0.5 h, then dropwise add 4.57 g of carbon disulfide. After the addition is complete, continue the reaction for 1 h, then remove the ice bath and continue the reaction for 1 h under the water bath conditions of 45 - 50 °C. Finally, filter and collect the yellow precipitate formed by the reaction, wash it with absolute ethanol and dry it to obtain antimony diallyldithiocarbamate. Disperse 10 g of halloysite nanotubes in 1000 ml of ethanol, then add 150 ml of ammonia water and 100 ml of deionized water. Stir for 24 h, then add 10 ml of 3-(methacryloyloxy)propyltrimethoxysilane and continue stirring and reacting for 48 h. After the reaction is completed, centrifuge to collect the precipitate and dry it to obtain functionalized halloysite nanotubes. Disperse 10 g of functionalized halloysite nanotubes in 200 ml of xylene, then add 5 g of antimony diallyldithiocarbamate and 0.01 g of free radical initiator AIBN. Stir and react under the water bath conditions of 60 °C for 5 h, then filter, collect the product, wash it with absolute ethanol and dry it.

[0088] Comparative Example 4:

[0089] It is basically the same as Example 1, except that halloysite nanotubes are directly added, that is, the halloysite nanotubes are not subjected to modification treatment.

[0090] Performance Test

[0091] Apply the glazes in Examples 1 - 6 and Comparative Examples 1 - 4 of the present invention onto 95 alumina ceramic substrates respectively, with the coating thickness of 10 ± 1 μm. Then dry the substrates and put them into a muffle furnace. First, heat them at a rate of 1 °C / min to 700 °C and hold for 1.5 h, then heat them at a rate of 5 °C / min to 1200 °C and sinter for 2 h to obtain specimens;

[0092] Use an SDC - 100 type contact angle measuring instrument to measure the static contact angle between the surface of the specimen and water.

[0093] Photodegradation test: The initial concentration of the prepared methylene blue solution is 50 mg / L, and the pH value is controlled at 6.5. Put the specimen into the methylene blue solution, and magnetically stir and disperse it for 30 min in a dark environment to reach the adsorption equilibrium. Then irradiate it with a 15 w ultraviolet lamp, and the distance between the ultraviolet lamp and the liquid surface is fixed at 15 cm. Take samples every 30 min, use an ultraviolet spectrophotometer to measure the absorption spectrum of the solution in the wavelength range of 200 - 800 nm, and select the absorbance at the maximum absorption peak of 664 nm (the main absorption peak of methylene blue) in the absorption spectrum to calculate the degradation rate of the specimen to the methylene blue solution.

[0094] The test results are shown in Table 1 below:

[0095] Table 1:

[0096]

[0097] As can be seen from Table 1 above, the static contact angle on the surface of the test piece is above 140°, and it has extremely high catalytic degradation efficiency for methylene blue, and can achieve anti-fouling flashover through the catalytic degradation of pollutants.

[0098] From the comparison of Examples 1-6, it can be seen that as the content of modified halloysite nanotubes increases, the catalytic degradation efficiency of the test piece for methylene blue first increases and then remains unchanged;

[0099] From the comparison of Example 1 and Comparative Example 1, it can be seen that the addition of modified halloysite nanotubes plays a positive role in increasing the static contact angle on the surface of the test piece and the catalytic degradation efficiency for methylene blue.

[0100] From the comparison of Example 1 and Comparative Examples 2-3, it can be seen that the addition of antimony diallyldithiocarbamate and 2-vinyl-4,6-diamino-1,3,5-triazine during the preparation of modified halloysite nanotubes plays a positive role in increasing the catalytic degradation efficiency of the test piece for methylene blue.

[0101] From the comparison of Example 1 and Comparative Example 4, it can be seen that although directly adding halloysite nanotubes can increase the static contact angle on the surface of the test piece, it has basically no catalytic degradation effect on methylene blue, and the decrease in the concentration of methylene blue may be due to the adsorption effect of the rough structure on the glaze surface.

[0102] The above examples are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing examples, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. An anti-fouling flashover ceramic insulator, characterized in that, It consists of a ceramic matrix and a glaze layer; By weight, the glaze layer is prepared from the following raw materials: 40 - 50 parts of potassium feldspar, 10 - 15 parts of Suzhou clay, 10 - 15 parts of calcite, 15 - 20 parts of quartz, 1 - 5 parts of alumina, 1 - 5 parts of magnesia, 5 - 10 parts of modified halloysite nanotubes; The modified halloysite nanotubes are loaded with a metal dialkyldithiocarbamate - aminotriazine copolymer.

2. The anti-fouling flashover ceramic insulator according to claim 1, characterized in that, The metal dialkyldithiocarbamate is zinc dialkyldithiocarbamate and / or antimony dialkyldithiocarbamate.

3. The anti-fouling flashover ceramic insulator according to claim 2, wherein The structural formula of the metal dialkyldithiocarbamate is as follows: R1 and R2 are the same or different, each independently an alkenyl group, M is Zn or Sb, and n is 2, 3 or 4.

4. The anti-fouling flashover ceramic insulator according to claim 3, wherein R1 and R2 are the same.

5. The anti-fouling flashover ceramic insulator according to claim 4, characterized in that, R1 and R2 are C2 - C6 alkenyl groups.

6. The anti-fouling flashover ceramic insulator according to claim 5, wherein, The aminotriazine is 2 - vinyl - 4,6 - diamino - 1,3,5 - triazine and / or 2 - allyl - 4,6 - diamino - 1,3,5 - triazine.

7. The anti-fouling flashover ceramic insulator according to claim 6, wherein, The preparation method of the modified halloysite nanotubes is as follows: Disperse the halloysite nanotubes in ethanol, then add ammonia water and deionized water, stir evenly and then add 3 - (isobutenyloxy)propyltrimethoxysilane for reaction. After the reaction, collect the precipitate and dry to obtain functionalized halloysite nanotubes. Disperse the functionalized halloysite nanotubes in an organic solvent, then add the metal dialkyldithiocarbamate, aminotriazine and a radical initiator, stir and react, collect the product, wash and dry.

8. The anti-fouling flashover ceramic insulator according to claim 7, wherein, The mass ratio of the functionalized halloysite nanotubes, the metal dialkyldithiocarbamate and the aminotriazine is 1:0.1 - 1:0.1 - 1.

9. The anti-fouling flashover ceramic insulator according to claim 1, wherein The ceramic matrix is made of alumina.

10. A preparation method of an anti-fouling flashover ceramic insulator as described in any one of claims 1-9, characterized in that, Mix potassium feldspar, Suzhou clay, calcite, quartz, alumina, magnesia, modified halloysite nanotubes and deionized water and ball - mill to obtain a glaze. Apply the glaze to the ceramic matrix to obtain a rough blank. Dry the rough blank and then put it into a muffle furnace. First, heat it to 600 - 800 °C and keep it warm for 1 - 2 h, then heat it to 1100 - 1200 °C and sinter for 1 - 5 h.

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