CN113205932A - Low-temperature-resistant anti-pollution-flashover ceramic insulator and manufacturing process thereof - Google Patents
Low-temperature-resistant anti-pollution-flashover ceramic insulator and manufacturing process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of insulators, and provides a low-temperature-resistant anti-pollution-flashover porcelain insulator and a manufacturing process thereof. According to the invention, the polymer is used for coating the modified nano particles and the water reducing agent containing the amino acid ionic liquid, and the polymer and the water reducing agent are synergistic, so that the comprehensive performance of the porcelain insulator is improved; the polyester, the modified nanoparticles and the olefin are copolymerized to obtain the uniformly dispersed polymer-coated modified nanoparticles, and the insulator raw material is subjected to ball milling twice, so that the binding property between organic matters and inorganic matters in the insulator raw material can be improved, the ball milling efficiency is improved, and the ball milling effect is improved. The porcelain insulator prepared by the invention has good electrical property, mechanical property, hydrophobic property and temperature resistance.
Description
Technical Field
The invention relates to the technical field of insulators, in particular to a low-temperature-resistant anti-pollution-flashover porcelain insulator and a manufacturing process thereof.
Background
The porcelain insulator provides supporting and insulating functions for the power transmission line, so that the requirements on mechanical strength and insulating strength are high, the natural environment of China is relatively complex, and the porcelain insulator is mostly used in outdoor or even field environments, so that the porcelain insulator product is also required to be capable of adapting to complex environmental conditions.
The working environment and working conditions of the insulator product are extremely harsh and are affected by factors such as cold and hot sudden change, intense heat, severe cold, high acidity and alkalinity, high pollution and the like. In the operation process of the insulator product, the insulator product not only needs to bear power frequency voltage under normal operation conditions, but also can withstand the transient overvoltage influence generated by lightning impulse under severe weather conditions; the weight of the lead is borne, and the lead is also subjected to extreme factors such as the icing state of the lead and the violent shaking of the lead under the action of wind power, and is subjected to severe heat and severe cold. The insulator product can generate a medium degradation phenomenon under the action of long-term working voltage and working load, namely the performance of the insulator product is reduced along with the prolonging of the service time, and finally the product is degraded.
With the development of the electric power industry in China, the requirements of extremely cold regions on porcelain insulators are increasing. The ceramic insulator is used for ceramic insulators used in extremely cold regions, needs to bear severe working environments such as low-temperature freezing, lightning impulse, medium deterioration and the like, and has good freeze-thaw resistance, so that the problems of freeze-thaw, aging, strength reduction and the like are avoided.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provides a low-temperature-resistant anti-pollution-flashover porcelain insulator and a manufacturing process thereof. The purpose of the invention is realized based on the following technical scheme:
the invention aims to provide a low-temperature-resistant and pollution-flashover-resistant porcelain insulator, which comprises an insulator body and a glaze layer, wherein the insulator body comprises the following raw materials in parts by weight: 15-25 parts of quartz, 15-25 parts of ginger sludges, 10-20 parts of tacrine pond sludge, 10-20 parts of Zuoyun soil, 5-15 parts of wollastonite, 5-15 parts of Hubei sludge, 5-15 parts of polymer-coated modified nanoparticles, 3-10 parts of zirconium oxide, 3-10 parts of boric acid, 1-5 parts of boron phosphide, 1-5 parts of silane coupling agents and 0.7-2 parts of water reducing agents; the glaze layer comprises the following raw materials in parts by weight: 12-20 parts of quartz, 12-20 parts of kaolin, 8-15 parts of aluminum oxide, 5-10 parts of zirconium silicate, 5-10 parts of talcum powder, 2-8 parts of polymer-coated modified nano particles, 2-8 parts of barium titanate and 1-6 parts of zinc oxide; the polymer comprises polyester and polyolefin, the monomer of the polyolefin comprises one or more of ethylene, propylene, styrene and chloroethylene, and the raw material of the nano particles of the modified nano particles comprises one or more of graphene oxide, nano silicon dioxide, nano titanium dioxide, nano magnesium oxide, nano aluminum oxide, nano zinc oxide, nano hydrotalcite, nano silicon nitride, nano silicon carbide and nano boron nitride; the water reducing agent contains amino acid ionic liquid.
The feldspar is used as one of raw materials in the traditional porcelain insulator, belongs to ridge raw materials and is not beneficial to uniform distribution in pug, and therefore mechanical, electrical and thermal properties of the porcelain insulator cannot be fully exerted. The formula of the invention widely adopts universal raw materials in most regions, and has wide application range; the variety of raw materials is multiple, and the influence caused by quality fluctuation of a single raw material is reduced; the formula contains silicon dioxide, aluminum oxide and potassium oxide in proper proportion, a large amount of clay or feldspar in the traditional formula is not needed, and the prepared insulator material is good in insulating property and mechanical property. The quartz, ginger flushing mud, merry pond mud and left cloud soil are main components forming a glass network in the insulator, and are beneficial to improving the compactness and hardness of the network.
The polyester has good fiber forming property, mechanical property, wear resistance, creep resistance, low water absorption and electrical insulation property, and can greatly improve the mechanical property of the insulator. The polyvinyl chloride has poor stability to light and heat, does not have a fixed melting point, and has good mechanical properties and excellent dielectric properties. The polystyrene has good electrical insulation performance, easy coloring, good processing fluidity, good rigidity, good chemical corrosion resistance and the like. The common polystyrene has the defects of brittleness, low impact strength, easy occurrence of stress cracking, poor heat resistance, boiling water resistance and the like. The polyethylene and polypropylene material has excellent dielectric property and volume resistance up to 1015～1020Omega.m, has good mechanical properties. Wherein, the tensile strength of the polypropylene is higher than that of the high-density polyethylene, the cold resistance of the polyethylene is excellent, the cold brittleness temperature is-70 ℃, and the low-temperature impact resistance of the polypropylene is poor. The modified nano particles have enhanced surface lipophilicity and can be effectively combined with other organic components in the polyolefin material, so that the compactness of the material is improved. The addition of the modified nanoparticles creates more traps within the polyolefin material that trap injected charges near the electrode-dielectric interface, reducing the local electric field while impeding the movement of carriers, thereby increasing resistivity. Ethylene, propylene, vinyl chloride and styrene are copolymerized, the advantages of various polyolefins can be combined, and polyester and modified nanoparticles are added into the copolymer to enhance the electrical property and the mechanical property of the insulator materialPerformance, low temperature resistance and acid and alkali resistance.
The boric acid can improve the heat resistance of the insulator, improve the mechanical strength and shorten the melting time; meanwhile, the glass is used as a fluxing agent to promote the melting of quartz, ginger sludges, merry pond sludge, left cloud soil and the like to form a glass network, so that the heat loss of unit insulator products is reduced. Boron oxide generated by boric acid decomposition does not generate gas in the melting process, so that air holes in the sintering process of the insulator are reduced, and the mechanical bending strength of the insulator is enhanced; the shrinkage rate of the green body can be effectively reduced, the moisture absorption expansion of the porcelain insulator can be reduced, the later-stage dry cracking of the ceramic green body can be prevented, the ceramic green body has higher mechanical strength and lower dielectric loss, the maturing speed of the sintering process can be accelerated, and the heat loss of unit insulator products is greatly reduced.
Wollastonite has good insulativity, good dielectric property, high heat resistance, high chemical corrosion resistance and high weather resistance, has stable size, glass and pearl luster, low water absorption rate and oil absorption value, excellent mechanical property and electrical property and a certain reinforcing effect, and can be used as a reinforcing filler of a porcelain insulator. Wollastonite is added, so that the shrinkage rate of the green body can be effectively reduced, the moisture absorption expansion of the green body can be reduced, and the later-stage dry cracking and the like of the ceramic green body are prevented; wollastonite-containing bodies also have higher mechanical strength and lower dielectric loss. The blank body of wollastonite is introduced, the curing speed is accelerated in the sintering process, the heat loss of unit products is greatly reduced, the sintering period is shortened, and the effects of energy conservation and consumption reduction are achieved.
Preferably, the anion of the amino acid ionic liquid comprises one or more of glycine, serine, proline, alanine, phenylalanine, glutamic acid and arginine, and the cation comprises one or more of imidazoles, quaternary ammonium and quaternary phosphorus.
Preferably, the content of polyester in the polymer-coated modified nanoparticle composite is 5-30 wt%, the content of modified nanoparticles is 1-18 wt%, and the particle size of the nanoparticles is 50-800 nm.
Preferably, the modifying treatment agent of the modified nanoparticles comprises stearate, calcium carbonate whisker, trimethylolpropane and a silane coupling agent, the stearate comprises one or more of sodium stearate, zinc stearate and calcium stearate, and the silane coupling agent comprises one or more of dodecylsilane, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, thiopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.
Preferably, the water reducing agent comprises the following raw materials in parts by weight: 5-20 parts of amino acid ionic liquid, 5-20 parts of polymethacrylic phosphate, 5-20 parts of polyphosphate, 5-20 parts of organic acid salt, 5-20 parts of sodium silicate or sodium metasilicate and 1-5 parts of sodium carbonate.
Preferably, the polymethine phosphate comprises one or more of amino trimethine phosphonate, ethylene diamine tetra methylene phosphonate, diethylene triamine penta methylene phosphonate, N-2 hydroxyethyl-N-dimethyl methylene phosphonate, ethoxyethyl diamine tetra methylene phosphonate, 1, 3-diamine-2-propanol tetra methylene phosphonate, (2-hydroxy) ethoxy ethyl amine dimethyl methylene phosphonate, piperazine dimethyl methylene phosphonate, aminoethyl piperazine trimethyl methylene phosphonate, glycine dimethyl methylene phosphonate, hydroxymethyl glycine dimethyl methylene phosphonate, glutamic dimethyl methylene phosphonate, formamido monomethyl phosphonate, acetamido-monomethyl phosphonate or ureido tetramethylene phosphonate.
Preferably, the organic acid salt comprises one or more of sodium citrate, sodium gluconate, sodium lactate, sodium acetate, potassium citrate, potassium gluconate, potassium lactate, potassium acetate, calcium citrate, calcium gluconate, calcium lactate, calcium acetate, amino acid chelated calcium, and calcium L-threonate, and the polyphosphate salt comprises a sodium salt or a potassium salt.
In another aspect of the present invention, a process for manufacturing a low temperature resistant and anti-pollution flashover porcelain insulator is provided, which comprises the following steps:
s1, preparation of polymer-coated modified nanoparticles: placing a polyolefin monomer, modified nanoparticles, a catalyst and a solvent into a closed drying reactor, carrying out constant-temperature polymerization reaction for 4-10 h at 50-80 ℃, adding a 5% HCl ethanol solution to terminate polymerization, filtering, washing and drying to obtain polymer-coated modified nanoparticles;
s2, ball milling: putting quartz, ginger flushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water to perform ball milling for 2-8 h, then adding polymer-coated modified nanoparticles, a silane coupling agent and a water reducing agent, and continuing to perform ball milling for 5-8 h;
s3, sieving and removing iron: sieving the slurry prepared in the step S3 by a sieve of 150-300 meshes until the residue is within 0.5 wt%, and then removing iron-containing impurities to obtain clean slurry;
s4, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s5, glazing: glazing the dried blank;
s6, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 300-450 ℃ at the speed of 5-20 ℃/h, then heating to 980-1050 ℃ at the speed of 50-100 ℃/h, preserving heat for 5-10 h, then heating to 1280-1350 ℃ at the speed of 20-50 ℃/h in a reducing atmosphere, preserving heat for 1-4 h, and then cooling to below 180 ℃ to obtain a porcelain insulator;
and S7, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
Preferably, the preparation method of the modified nanoparticle in step S1 includes:
s11, dispersing the nano particles and the stearate in water to form a dispersion liquid;
s12, uniformly mixing the calcium carbonate whisker, the trimethylolpropane, the silane coupling agent and ethanol, adding the dispersion liquid obtained in the step S11, heating and reacting at 50-100 ℃ for 1-5 hours, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate whisker, the trimethylolpropane and the silane coupling agent.
Preferably, the cooling rate of the cooling in the step S6 is 50-150 ℃/h.
The invention can obtain at least one of the following beneficial effects:
the invention utilizes the copolymerization of the polyester, the modified nanoparticles and the olefin, improves the dispersibility of the polyester and the nanoparticles in the polyolefin matrix, and fully exerts the improvement effect of the polyester and the nanoparticles on the electrical property and the mechanical property of the insulator material; the polymer coating layer and the silane coupling agent are compounded, so that the cohesiveness of an inorganic/organic interface in the insulator material is enhanced, the raw materials are effectively combined, and the compactness of the insulator material is greatly improved; the modified nano particles can greatly improve the hydrophobicity, mechanical property and electrical property of the material. In addition, the water reducing agent component contains amino acid ionic liquid, contains a large amount of N atoms and carboxyl groups, can be stably coordinated with high-valence metals, and the hydroxyl groups can enhance the hydrophilicity and enhance the fluidity of the slurry. The water reducing agent has obvious water reducing effect on porcelain insulator slurry under the conditions of low consumption, low water content and high-valence metal ion-containing water quality, shows outstanding fluidity and dispersive water reducing effect, and further improves various performances of porcelain insulators, wherein the porcelain insulators after high-temperature firing have flat surfaces, no cracks and no defects. The invention utilizes the polymer to coat the modified nano particles and the water reducing agent containing the amino acid ionic liquid, and the polymer and the water reducing agent have synergistic effect, so that the comprehensive performance of the porcelain insulator is improved.
According to the method, the polyester, the modified nanoparticles and the olefin are copolymerized to obtain the uniformly dispersed polymer-coated modified nanoparticles, the insulator raw material is subjected to ball milling twice, namely, the inorganic raw material is subjected to ball milling for a certain time, and then the raw material containing organic substances and the water reducing agent are added for continuous ball milling, so that the binding property between the organic substances and the inorganic substances in the insulator raw material can be improved, the ball milling efficiency is improved, the ball milling effect is improved, the uniformly dispersed slurry is obtained, and the ceramic insulator with excellent comprehensive performance is obtained through the programmed heating, firing and cooling steps. The porcelain insulator prepared by the invention has good electrical property, mechanical property, hydrophobic property and temperature resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the mass ratio of nanoparticles to water in the preparation of the dispersion was 1: 50, the mass ratio of the calcium carbonate crystal whisker, the trimethylolpropane, the silane coupling agent and the ethanol is 1: 10: 4: 120, volume ratio of dispersion liquid to mixed liquid is 1: 1; the catalyst for the polymerization reaction is a composite catalyst of zirconium propionitrile metallocene chloride-methylaluminoxane, the dosage of the catalyst is 5 percent of the mass of the monomer, and the dosage of the solvent cyclohexane is 2 times of the mass of the monomer.
Example 1
A low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises an insulator body and a glaze layer. The insulator body comprises the following raw materials in parts by weight: 15 parts of quartz, 25 parts of ginger flushing mud, 10 parts of tacrine pond mud, 10 parts of Zuoyun soil, 5 parts of wollastonite, 5 parts of Hubei mud, 5 parts of polymer-coated modified nano particles, 3 parts of zirconium oxide, 3 parts of boric acid, 1 part of boron phosphide, 1 part of dodecyl silane and 0.7 part of water reducing agent; the glaze layer comprises the following raw materials in parts by weight: 12 parts of quartz, 20 parts of kaolin, 8 parts of alumina, 5 parts of zirconium silicate, 5 parts of talcum powder, 2 parts of polymer-coated modified nano particles, 2 parts of barium titanate and 1 part of zinc oxide. The content of polyester in the polymer-coated modified nanoparticles is 5 wt%, the content of the modified nanoparticles is 18 wt%, and the particle size is 50-800 nm; the water reducing agent comprises 5 parts of 1-butyl-3-methylimidazole glycinate, 20 parts of amino trimethylene sodium phosphonate, 5 parts of sodium tripolyphosphate, 5 parts of amino acid chelated calcium, 5 parts of sodium silicate and 1 part of sodium carbonate.
A manufacturing process of a low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises the following steps:
s1, preparation of modified nanoparticles: dispersing graphene oxide, nano boron nitride and sodium stearate (mass ratio is 1: 1: 0.025) in water to form a dispersion liquid; and (3) uniformly mixing the calcium carbonate crystal whisker, the trimethylolpropane, the aminopropyltriethoxysilane and the ethanol to obtain a mixed solution, adding the dispersion liquid obtained in the step S11, heating and reacting for 5 hours at 55 ℃, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate crystal whisker.
S2, preparation of polymer-coated modified nanoparticles: placing monomer ethylene, polymethyl methacrylate, modified nanoparticles, a catalyst and a solvent in a closed dry reactor, carrying out constant-temperature polymerization reaction for 8 hours at 55 ℃, adding an ethanol solution of 5% HCl to terminate polymerization, filtering, washing and drying to obtain polymer-coated modified nanoparticles;
s3, ball milling: putting quartz, ginger flushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water to perform ball milling for 2 hours, then adding polymer-coated modified nanoparticles, a silane coupling agent and a water reducing agent, and continuing to perform ball milling for 8 hours;
s4, sieving and removing iron: s3, sieving the slurry prepared in the step by a 150-mesh sieve to obtain the residue within 0.5 wt%, and then removing iron-containing impurities to obtain clean slurry;
s5, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s6, glazing: glazing the dried blank;
s7, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 300 ℃ at the speed of 5 ℃/h, then heating to 980 ℃ at the speed of 50 ℃/h, preserving heat for 5h, then heating to 1280 ℃ at the speed of 20 ℃/h in a reducing atmosphere, preserving heat for 1h, and then cooling to below 180 ℃ at the cooling speed of 50 ℃/h to obtain a porcelain insulator;
and S8, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
Example 2
A low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises an insulator body and a glaze layer. The insulator body comprises the following raw materials in parts by weight: 25 parts of quartz, 15 parts of ginger flushing mud, 20 parts of moenomas pond mud, 20 parts of Zuoyun soil, 15 parts of wollastonite, 15 parts of Hubei mud, 15 parts of polymer-coated modified nano particles, 10 parts of zirconium oxide, 10 parts of boric acid, 5 parts of boron phosphide, 5 parts of vinyl trimethoxy silane and 2 parts of a water reducing agent; the glaze layer comprises the following raw materials in parts by weight: 20 parts of quartz, 12 parts of kaolin, 15 parts of alumina, 10 parts of zirconium silicate, 10 parts of talcum powder, 8 parts of polymer-coated modified nano particles, 8 parts of barium titanate and 6 parts of zinc oxide. The content of polyester in the polymer-coated modified nanoparticles is 30 wt%, the content of the modified nanoparticles is 2 wt%, and the particle size of the nanoparticles is 50-500 nm; the water reducing agent comprises 10 parts of 1-butyl-2, 3-dimethyl imidazole proline salt, 10 parts of methyl imidazole proline salt, 5 parts of glutamic acid dimethyl methylene phosphonic acid sodium, 20 parts of potassium polymetaphosphate, 10 parts of sodium citrate, 10 parts of sodium gluconate, 20 parts of sodium metasilicate and 5 parts of sodium carbonate.
A manufacturing process of a low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises the following steps:
s1, preparation of modified nanoparticles: dispersing nano silicon carbide, nano titanium dioxide and zinc stearate (the mass ratio is 1: 1: 0.01) in water to form dispersion liquid; and (3) uniformly mixing the calcium carbonate whisker, the trimethylolpropane and the vinyl trimethoxy silane with ethanol, adding the dispersion liquid obtained in the step S11, heating and reacting for 1h at 100 ℃, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate whisker.
S2, preparation of polymer-coated modified nanoparticles: placing propylene, styrene (mass ratio is 3: 2), poly-p-hydroxybenzoate, modified nanoparticles, a catalyst and a solvent in a closed drying reactor, carrying out polymerization reaction for 4 hours at a constant temperature of 75 ℃, adding an ethanol solution of 5% HCl to terminate polymerization, filtering, washing and drying to obtain polymer-coated modified nanoparticles;
s3, ball milling: putting quartz, ginger slushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water into the ball mill, carrying out ball milling for 8 hours, then adding polymer-coated modified nano particles, a silane coupling agent and a water reducing agent, and continuing ball milling for 5 hours;
s4, sieving and removing iron: s3, sieving the slurry prepared in the step by a 300-mesh sieve to obtain the residue within 0.5 wt%, and then removing iron-containing impurities to obtain clean slurry;
s5, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s6, glazing: glazing the dried blank;
s7, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 450 ℃ at the speed of 20 ℃/h, then heating to 1050 ℃ at the speed of 100 ℃/h, preserving heat for 10h, then heating to 1350 ℃ at the speed of 50 ℃/h in a reducing atmosphere, preserving heat for 4h, and then cooling to below 160 ℃ at the cooling speed of 150 ℃/h to obtain a porcelain insulator;
and S8, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
Example 3
A low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises an insulator body and a glaze layer. The insulator body comprises the following raw materials in parts by weight: 22 parts of quartz, 20 parts of ginger sludges, 15 parts of moenlian pond sludge, 15 parts of Zuoyun soil, 10 parts of wollastonite, 10 parts of Hubei sludge, 10 parts of polymer-coated modified nanoparticles, 8 parts of zirconia, 6 parts of boric acid, 3 parts of boron phosphide, 1.5 parts of glycidyl ether oxypropyltrimethoxysilane, 1.5 parts of thiopropyltrimethoxysilane and 1.5 parts of a water reducing agent; the glaze layer comprises the following raw materials in parts by weight: 16 parts of quartz, 18 parts of kaolin, 12 parts of aluminum oxide, 8 parts of zirconium silicate, 8 parts of talcum powder, 6 parts of polymer-coated modified nano particles, 6 parts of barium titanate and 3 parts of zinc oxide. The content of polyester in the polymer-coated modified nanoparticles is 20 wt%, the content of the modified nanoparticles is 12.5 wt%, and the particle size is 200-800 nm; the water reducing agent comprises 6 parts of 1-ethyl-3-methylimidazolyl alanine salt, 6 parts of butyl sulfonic acid-triethylamine alanine salt, 6 parts of ethylene diamine tetra methylene potassium phosphate, 5 parts of ethoxy ethyl diamine tetra methylene sodium phosphate, 12 parts of sodium polyphosphate, 5 parts of sodium lactate, 5 parts of potassium citrate, 10 parts of sodium silicate and 3 parts of sodium carbonate.
A manufacturing process of a low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises the following steps:
s1, preparation of modified nanoparticles: dispersing nano magnesium oxide, nano aluminum oxide, nano boron nitride and calcium stearate (mass ratio is 1: 1: 1: 0.05) in water to form dispersion liquid; uniformly mixing calcium carbonate whisker, trimethylolpropane, glycidoxypropyltrimethoxysilane and thiopropyltrimethoxysilane with ethanol, adding the dispersion liquid obtained in the step S11, heating to react for 3 hours at 65 ℃, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate/glycidoxypropyltrimethoxysilane/thiopropyltrimethoxysilane/solid product.
S2, preparation of polymer-coated modified nanoparticles: placing ethylene, chloroethylene (mass ratio is 2: 1), polydiallyl terephthalate, modified nanoparticles, a catalyst and a solvent into a closed drying reactor, carrying out polymerization reaction at constant temperature of 65 ℃ for 5 hours, adding an ethanol solution of 5% HCl to terminate polymerization, filtering, washing and drying to obtain polymer-coated modified nanoparticles;
s3, ball milling: putting quartz, ginger slushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water into the ball mill, carrying out ball milling for 5 hours, then adding polymer-coated modified nano particles, a silane coupling agent and a water reducing agent, and continuing ball milling for 6 hours;
s4, sieving and removing iron: sieving the slurry prepared in the step S3 by a 200-mesh sieve until the residue is within 0.3 wt%, and then removing iron-containing impurities to obtain clean slurry;
s5, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s6, glazing: glazing the dried blank;
s7, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 400 ℃ at the speed of 10 ℃/h, then heating to 1000 ℃ at the speed of 60 ℃/h, preserving heat for 8h, then heating to 1300 ℃ at the speed of 30 ℃/h in a reducing atmosphere, preserving heat for 2h, and then cooling to below 130 ℃ at the cooling speed of 100 ℃/h to obtain a porcelain insulator;
and S8, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
Example 4
A low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises an insulator body and a glaze layer. The insulator body comprises the following raw materials in parts by weight: 18 parts of quartz, 22 parts of ginger sludges, 12 parts of moenomas pond sludge, 12 parts of Zuoyun soil, 12 parts of wollastonite, 8 parts of Hubei sludge, 8 parts of polymer-coated modified nanoparticles, 5 parts of zirconia, 5 parts of boric acid, 3.5 parts of boron phosphide, 2 parts of 3-aminopropyltrimethoxysilane, 2 parts of gamma-aminopropyltrimethoxysilane and 1 part of water reducing agent; the glaze layer comprises the following raw materials in parts by weight: 14 parts of quartz, 15 parts of kaolin, 10 parts of alumina, 6 parts of zirconium silicate, 6 parts of talcum powder, 3 parts of polymer-coated modified nano particles, 3 parts of barium titanate and 2 parts of zinc oxide. The content of polyester in the polymer-coated modified nanoparticles is 10 wt%, the content of the modified nanoparticles is 5 wt%, and the particle size of the nanoparticles is 100-600 nm; the water reducing agent comprises 8 parts of methyl tributyl phosphine glutamate, 7 parts of methyl tributyl phosphine arginine salt, 5 parts of hydroxymethyl glycine dimethyl idene sodium phosphonate, 5 parts of ureido tetramethyl idene potassium phosphonate, 5 parts of aminoethyl piperazine trimethyl idene sodium phosphonate, 15 parts of potassium polymetaphosphate, 5 parts of potassium gluconate, 5 parts of potassium lactate, 5 parts of L-calcium threonate, 15 parts of sodium silicate and 4 parts of sodium carbonate.
A manufacturing process of a low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises the following steps:
s1, preparation of modified nanoparticles: dispersing nano zinc oxide, nano silicon nitride and sodium stearate (mass ratio is 1: 1: 0.1) in water to form dispersion liquid; and (3) uniformly mixing the calcium carbonate crystal whisker, the trimethylolpropane and the gamma-aminopropyltrimethoxysilane with ethanol, adding the dispersion liquid obtained in the step S11, heating and reacting for 2 hours at 85 ℃, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate crystal whisker.
S2, preparation of polymer-coated modified nanoparticles: placing ethylene, vinyl chloride, styrene (mass ratio is 2: 1: 1), polybutylene terephthalate, modified nanoparticles, a catalyst and a solvent into a closed drying reactor, carrying out polymerization reaction at a constant temperature of 70 ℃ for 6 hours, adding an ethanol solution of 5% HCl to terminate polymerization, filtering, washing and drying to obtain polymer-coated modified nanoparticles;
s3, ball milling: putting quartz, ginger slushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water into the ball mill, carrying out ball milling for 6 hours, then adding polymer-coated modified nano particles, a silane coupling agent and a water reducing agent, and continuing ball milling for 6 hours;
s4, sieving and removing iron: s3, sieving the slurry prepared in the step by a 250-mesh sieve to obtain the residue within 0.2 wt%, and then removing iron-containing impurities to obtain clean slurry;
s5, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s6, glazing: glazing the dried blank;
s7, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 350 ℃ at the speed of 8 ℃/h, then heating to 1030 ℃ at the speed of 80 ℃/h, preserving heat for 7h, then heating to 1330 ℃ at the speed of 40 ℃/h in a reducing atmosphere, preserving heat for 2h, and then cooling to below 80 ℃ at the cooling speed of 80 ℃/h to obtain a porcelain insulator;
and S8, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
Example 5
A low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises an insulator body and a glaze layer. The insulator body comprises the following raw materials in parts by weight: 20 parts of quartz, 18 parts of ginger flushing mud, 13 parts of moenomas pond mud, 16 parts of Zuoyun soil, 12 parts of wollastonite, 10 parts of Hubei mud, 9 parts of polymer-coated modified nano particles, 7 parts of zirconia, 5 parts of boric acid, 2 parts of boron phosphide, 1.6 parts of vinyltrimethoxysilane, 1.6 parts of 3-aminopropyltrimethoxysilane and 1.2 parts of a water reducing agent; the glaze layer comprises the following raw materials in parts by weight: 18 parts of quartz, 15 parts of kaolin, 10 parts of alumina, 6.5 parts of zirconium silicate, 7 parts of talcum powder, 5 parts of polymer-coated modified nano particles, 5 parts of barium titanate and 2.5 parts of zinc oxide. The content of polyester in the polymer-coated modified nanoparticles is 15 wt%, the content of the modified nanoparticles is 8.3 wt%, and the particle size is 50-600 nm; the water reducing agent comprises 3 parts of 1-butyl-2, 3-dimethyl imidazole phenylalanine salt, 5 parts of 1-dodecyl-3-methyl imidazole serine salt, 5 parts of methyl tributyl phosphine glutamate, 6 parts of formamido-methylene phosphonic acid sodium, 6 parts of piperazine dimethyl methylene phosphonic acid sodium, 8 parts of sodium polyphosphate, 4 parts of sodium citrate, 4 parts of amino acid chelated calcium, 4 parts of L-threonic acid calcium, 10 parts of sodium metasilicate and 2.2 parts of sodium carbonate.
A manufacturing process of a low-temperature-resistant and pollution flashover-resistant porcelain insulator comprises the following steps:
s1, preparation of modified nanoparticles: dispersing graphene oxide, nano titanium dioxide, nano magnesium oxide and zinc stearate (the mass ratio is 1: 1: 1: 0.075) in water to form a dispersion liquid; uniformly mixing calcium carbonate whisker, trimethylolpropane, vinyl trimethoxy silane, 3-aminopropyl trimethoxy silane and ethanol, adding the dispersion liquid obtained in the step S11, heating and reacting at 75 ℃ for 2.5h, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate/vinyl trimethoxy silane/3-aminopropyl trimethoxy silane/ethanol composite material.
S2, preparation of polymer-coated modified nanoparticles: putting ethylene, propylene, styrene (mass ratio is 2: 2: 1), polyethylene terephthalate, modified nanoparticles, a catalyst and a solvent into a closed drying reactor, carrying out polymerization reaction at constant temperature of 65 ℃ for 7 hours, adding an ethanol solution of 5% HCl to terminate polymerization, filtering, washing and drying to obtain polymer-coated modified nanoparticles;
s3, ball milling: putting quartz, ginger slushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water to perform ball milling for 6 hours, then adding polymer-coated modified nanoparticles, a silane coupling agent and a water reducing agent, and continuing to perform ball milling for 7 hours;
s4, sieving and removing iron: s3, sieving the slurry prepared in the step by a 250-mesh sieve to obtain the residue within 0.3 wt%, and then removing iron-containing impurities to obtain clean slurry;
s5, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s6, glazing: glazing the dried blank;
s7, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 380 ℃ at the speed of 12 ℃/h, then heating to 1010 ℃ at the speed of 75 ℃/h, preserving heat for 8h, then heating to 1310 ℃ at the speed of 35 ℃/h in a reducing atmosphere, preserving heat for 2.5h, and then cooling to below 120 ℃ at the cooling speed of 120 ℃/h to obtain a porcelain insulator;
and S8, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
Comparative example 1
The ionic liquid in the water reducing agent was removed, as in example 5.
Comparative example 2
Sodium metasilicate was used as the water reducing agent, and the rest was the same as in example 5.
Comparative example 3
The polymer-coated modified nanoparticles in the insulator body were removed, as in example 5.
Comparative example 4
The polymer-coated modified nanoparticles in the glaze layer were removed as in example 5.
Comparative example 5
The same procedure as in example 5 was repeated except that the insulator body and the glaze layer were not modified with respect to the nanoparticles.
Comparative example 6
The modified nanoparticles of the insulator body and glaze layer were removed, as in example 5.
Comparative example 7
The insulator body and the glaze layer were removed of polyester, as in example 5.
Initial viscosity and change in fluidity of the slurry obtained in examples 1 to 5 and comparative examples 1 to 2 were measured, the slurry was sintered after molding, and the surface condition of the obtained porcelain insulator was observed, and the results are shown in table 1.
TABLE 1
(note: the total water content of the slurry includes water in the water reducing agent and water in different water qualities)
As can be seen from the data in Table 1, compared with the comparative example 2, the water reducing agent of the invention has excellent water reducing effect on deionized water and well water under the condition of low dosage, the slurry has good fluidity, and after the slurry is placed for a period of time, the slurry has small fluidity loss, small thixotropy and easy molding; and the surface of the porcelain insulator obtained after high-temperature firing is flat, has no cracks and is free from defects. Compared with the comparative example 1, the ionic liquid can greatly improve the water reducing effect of the water reducing agent on the slurry, and is beneficial to improving the surface property of the obtained porcelain insulator.
The porcelain insulators obtained in examples 1 to 5 and comparative examples 1 to 7 were subjected to performance tests, and the results are shown in table 2.
TABLE 2
As can be seen from the data in Table 1, the porcelain insulator obtained by the invention has excellent hydrophobicity, mechanical property and electrical property, and can well maintain the surface property after long-term low-temperature treatment, which shows that the porcelain insulator has good low-temperature resistance and can be applied to alpine regions. Compared with the comparative examples 1-2, the ionic liquid in the water reducing agent has certain influence on the surface property of the insulator, so that the low-temperature resistance of the insulator is influenced, and the removal of the water reducing agent has great influence on various properties of the insulator, particularly hydrophobicity and low-temperature resistance. Compared with comparative examples 3-4, the polymer coated modified nano particles can greatly improve the comprehensive performance of the insulator; the polymer-coated modified nanoparticles in the insulator body have the largest influence on the mechanical property and the electrical property of the insulator body, and the polymer-coated modified nanoparticles in the glaze layer have the largest influence on the hydrophobicity and the low-temperature resistance of the insulator body. Compared with the comparative examples 5-6, the nano particle modification treatment has a large influence on the hydrophobic performance of the insulator, and the removal of the modified nano particles has a large influence on various performances of the insulator, particularly the mechanical performance and the electrical performance. Compared with comparative example 7, the polyester has a large influence on the mechanical properties of the insulator, and the hydrophobicity has almost no influence.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. The low-temperature-resistant and pollution-flashover-resistant porcelain insulator is characterized by comprising an insulator body and a glaze layer, wherein the insulator body comprises the following raw materials in parts by weight: 15-25 parts of quartz, 15-25 parts of ginger sludges, 10-20 parts of tacrine pond sludge, 10-20 parts of Zuoyun soil, 5-15 parts of wollastonite, 5-15 parts of Hubei sludge, 5-15 parts of polymer-coated modified nanoparticles, 3-10 parts of zirconium oxide, 3-10 parts of boric acid, 1-5 parts of boron phosphide, 1-5 parts of silane coupling agents and 0.7-2 parts of water reducing agents; the glaze layer comprises the following raw materials in parts by weight: 12-20 parts of quartz, 12-20 parts of kaolin, 8-15 parts of aluminum oxide, 5-10 parts of zirconium silicate, 5-10 parts of talcum powder, 2-8 parts of polymer-coated modified nano particles, 2-8 parts of barium titanate and 1-6 parts of zinc oxide; the polymer comprises polyester and polyolefin, the monomer of the polyolefin comprises one or more of ethylene, propylene, styrene and chloroethylene, and the raw material of the nano particles of the modified nano particles comprises one or more of graphene oxide, nano silicon dioxide, nano titanium dioxide, nano magnesium oxide, nano aluminum oxide, nano zinc oxide, nano hydrotalcite, nano silicon nitride, nano silicon carbide and nano boron nitride; the water reducing agent contains amino acid ionic liquid.
2. The porcelain insulator with low temperature resistance and pollution flashover resistance as claimed in claim 1, wherein anions of the amino acid ionic liquid comprise one or more of glycine, serine, proline, alanine, phenylalanine, glutamic acid and arginine, and cations comprise one or more of imidazoles, quaternary ammonium and quaternary phosphorus.
3. The low temperature and pollution flashover resistant porcelain insulator according to claim 1, wherein the content of the polyester in the polymer-coated modified nanoparticle composite is 5 to 30 wt%, the content of the modified nanoparticles is 1 to 18 wt%, and the particle size of the nanoparticles is 50 to 800 nm.
4. The low temperature and anti-pollution flashover resistant porcelain insulator according to claim 1, wherein the modifying treatment agent for the modified nanoparticles comprises one or more of stearate, calcium carbonate whisker, trimethylolpropane and silane coupling agent, the stearate comprises one or more of sodium stearate, zinc stearate and calcium stearate, and the silane coupling agent comprises one or more of dodecylsilane, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, thiopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.
5. The porcelain insulator with low temperature resistance and pollution flashover resistance according to claim 1, wherein the water reducing agent comprises the following raw materials in parts by weight: 5-20 parts of amino acid ionic liquid, 5-20 parts of polymethacrylic phosphate, 5-20 parts of polyphosphate, 5-20 parts of organic acid salt, 5-20 parts of sodium silicate or sodium metasilicate and 1-5 parts of sodium carbonate.
6. The low temperature and pollution flashover resistant porcelain insulator of claim 5 wherein said polymethine phosphate comprises one or more of amino trimethine phosphonate, ethylenediamine tetra-methylene phosphonate, diethylenetriamine penta-methylene phosphonate, N-2 hydroxyethyl-N-dimethyl-phosphonate, ethoxyethyl diamine tetra-methylene phosphonate, 1, 3-diamine-2-propanol tetra-methylene phosphonate, (2-hydroxy) ethoxyethylamine dimethyl-methylene phosphonate, piperazine dimethyl-methylene phosphonate, aminoethyl piperazine tri-methylene phosphonate, glycine dimethyl-methylene phosphonate, hydroxymethyl glycine dimethyl-methylene phosphonate, glutamic dimethyl-methylene phosphonate, formamido-methylene phosphonate, acetamido-methylene phosphonate or ureido-dimethyl-methylene phosphonate.
7. The low temperature and pollution flashover resistant porcelain insulator according to claim 5, wherein the organic acid salt comprises one or more of sodium citrate, sodium gluconate, sodium lactate, sodium acetate, potassium citrate, potassium gluconate, potassium lactate, potassium acetate, calcium citrate, calcium gluconate, calcium lactate, calcium acetate, amino acid chelated calcium, and calcium L-threonate, and the polyphosphate salt comprises a sodium salt or a potassium salt.
8. A manufacturing process of a low-temperature-resistant and pollution flashover-resistant porcelain insulator is characterized by comprising the following steps:
s1, preparation of polymer-coated modified nanoparticles: placing a polyolefin monomer, polyester, modified nanoparticles, a catalyst and a solvent into a closed dry reactor to perform constant-temperature polymerization reaction to obtain polymer-coated modified nanoparticles;
s2, ball milling: putting quartz, ginger flushing mud, merry pond mud, Zuoyun soil, wollastonite, Hubei mud, zirconia, boric acid and boron phosphide into a ball mill, adding water to perform ball milling for 2-8 h, then adding polymer-coated modified nanoparticles, a silane coupling agent and a water reducing agent, and continuing to perform ball milling for 5-8 h;
s3, sieving and removing iron: sieving the slurry prepared in the step S3 by a sieve of 150-300 meshes until the residue is within 0.5 wt%, and then removing iron-containing impurities to obtain clean slurry;
s4, sequentially carrying out mud pressing, staling, vacuum pugging, forming, blank trimming and drying to obtain a blank;
s5, glazing: glazing the dried blank;
s6, sintering: putting the blank into a kiln, taking the room temperature as an initial temperature, heating to 300-450 ℃ at the speed of 5-20 ℃/h, then heating to 980-1050 ℃ at the speed of 50-100 ℃/h, preserving heat for 5-10 h, then heating to 1280-1350 ℃ at the speed of 20-50 ℃/h in a reducing atmosphere, preserving heat for 1-4 h, and then cooling to below 180 ℃ to obtain a porcelain insulator;
and S7, performing cementing, curing, detecting and packaging on the obtained porcelain insulator of the porcelain insulator to obtain the porcelain insulator.
9. The porcelain insulator with low temperature resistance and pollution flashover resistance according to claim 8, wherein the preparation method of the modified nanoparticles in step S1 comprises the following steps:
s11, dispersing the nano particles and the stearate in water to form a dispersion liquid;
s12, uniformly mixing the calcium carbonate whisker, the trimethylolpropane, the silane coupling agent and ethanol, adding the dispersion liquid obtained in the step S11, heating and reacting at 50-100 ℃ for 1-5 hours, cooling, filtering to obtain a solid product, and drying to obtain the calcium carbonate whisker, the trimethylolpropane and the silane coupling agent.
10. The porcelain insulator with low temperature resistance and pollution flashover resistance as claimed in claim 1, wherein the cooling rate of the cooling in the step S6 is 50-150 ℃/h.
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