CN105097152A - Surface-modified porcelain insulator and preparation method thereof - Google Patents
Surface-modified porcelain insulator and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a surface-modified porcelain insulator. The method comprises the following steps: mixing a hydrolysable titanium source with a solution containing rare-earth metal elements for hydrolysis reaction, and preparing rare-earth-doped titanium dioxide-based sol; and coating the surface of the porcelain insulator with the rare-earth-doped titanium dioxide-based sol, drying the surface and then carrying out thermal treatment, so as to obtain the surface-modified porcelain insulator. According to the preparation method, the surface of the porcelain insulator is coated with a rare-earth-doped titanium dioxide film; due to the super hydrophilicity and the photocatalytic activity of the titanium dioxide film, the self-cleaning property and the easy-to-clean property of the film surface can be kept for a long period of time; the effect of reducing dirt accumulation is reached; and a pollution flashover accident is reduced, so that the pollution accumulation resistance of the porcelain insulator surface is improved; the electrical properties are also improved; the pollution flashover phenomenon caused by surface pollution accumulation is fundamentally reduced; in addition, the preparation method is simple in process, convenient to operate and low in cost; and the obtained surface-modified porcelain insulator is long in service life, and has a wide practical application prospect.
Description
Technical field
The present invention relates to electroceramics technical field, the particularly porcelain insulator relating to surface modification and preparation method thereof.
Background technology
Porcelain insulator, because of its excellent properties such as high stability, corrosion resistance, is directly subordinate to the insulating material be most widely used in insulator industry one.As the main body that various electric equipment supports and insulate, porcelain insulator is generally used for supporting or hanging high-pressure conductor.When air humidity is very high, or under the unfavourable weather conditions such as rainwater, mist, dew, snow, porcelain insulator surface pollution layer is moistening, its surface conductance increases severely, porcelain insulator leakage current is sharply increased, the flashover voltage of porcelain insulator reduces greatly, and even under operating voltage, flashover may occur, this phenomenon is called pollution flashover.
Pollution flashover refers to the dunghill of insulation of electrical installation surface attachment in humid conditions, and its soluble substance is water-soluble gradually, forms one deck conducting film at insulating surface, and the insulation level of insulator is reduced greatly, the strong electric discharge phenomena occurred under field of electric force effect.Along with the rising of the aggravation of industrial expansion, pollution, the increase of net capacity and grade of rated voltage, the impact that the pollution flashover accident of electric power system power transmission and transformation equipment outer insulation causes becomes increasingly conspicuous.
The domestic and international research about porcelain insulator Anti-pollution Flashover at present mainly launches in two: one is the configuration design improving insulator, and two is the surface propertys improving insulator.In the research improving insulator surface performance, the high-molecular organic material that surface energy is low, insulating properties is strong and pliability is good, as room temperature vulcanized silicone rubber, receives extensive concern.But high-molecular organic material is expensive, ageing resistance is poor, perishable, useful life is short, hinder its development.
Summary of the invention
Based on this, be necessary to provide that a kind of cost is low, the porcelain insulator of the surface modification of the antifouling work of long service life and preparation method thereof.
A preparation method for surface modification porcelain insulator, comprises the steps:
, there is hydrolysis by hydrolyzable titanium source and the mixing of the solution containing thulium, prepare rear-earth-doped titania colloidal solate in step one;
Step 2, is coated on porcelain insulator surface by described rear-earth-doped titania colloidal solate, heat-treats after drying, obtain the porcelain insulator of described surface modification.
The preparation method of the porcelain insulator of above-mentioned surface modification, the rear-earth-doped titanium deoxid film of one deck is applied at porcelain insulator surface, the Superhydrophilic of titanium deoxid film and photocatalytic activity make film surface keep automatically cleaning and easy cleaning for a long time, reach the effect the generation reducing pollution flashover accident that reduce filthy accumulation, thus the anti-contamination performance of porcelain insulator surface is improved, electric property also makes moderate progress, and fundamentally reduces the pollution flashover phenomenon that surperficial contamination causes.In addition, preparation method's technique of the porcelain insulator of above-mentioned surface modification is simple, and easy to operate, cost is low, long service life, has actual application prospect widely.
Wherein in an embodiment, in described hydrolyzable titanium source, solute is at least one in butyl titanate, tetraisopropyl titanate and titanium tetrachloride, and solvent is ethanol.
Wherein in an embodiment, in described hydrolyzable titanium source, the mole of titanium elements and the volume ratio of ethanol are 0.5 ~ 1.5mol:1L.
Wherein in an embodiment, in described rear-earth-doped titania colloidal solate, the mol ratio of titanium elements and thulium is 100:0.1 ~ 10.
Wherein in an embodiment, described containing in the solution of thulium, solute is the nitrate of thulium, and solvent is the mixed solvent of water and ethanol.
Wherein in an embodiment, the nitrate of described thulium is one or more in yttrium nitrate, lanthanum nitrate and cerous nitrate; In the mixed solvent of described water and ethanol, the volume ratio of water and ethanol is 1:1 ~ 1:5.
Wherein in an embodiment, before described step one, also comprise step: regulate the acid-base value of the described solution containing thulium to be less than or equal to 5 to pH.
Wherein in an embodiment, described rear-earth-doped titania colloidal solate is 1 ~ 10mL/m at the coated weight of porcelain insulator surface
2.
Wherein in an embodiment, the condition of described drying is dry 5 ~ 30min at 50 ~ 80 DEG C, and described heat treated condition is in 350 ~ 650 DEG C of process 2 ~ 6h.
A porcelain insulator for surface modification, adopts the preparation method of the porcelain insulator of above-mentioned surface modification to obtain.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method of the porcelain insulator of the surface modification of an execution mode.
Embodiment
For the ease of understanding the present invention, below with reference to relevant drawings, the present invention is described more fully.Preferred embodiment of the present invention is given in accompanying drawing.But the present invention can realize in many different forms, is not limited to embodiment described herein.On the contrary, provide the object of these embodiments be make the understanding of disclosure of the present invention more comprehensively thorough.
With reference to Fig. 1, the preparation method of the porcelain insulator of the surface modification of an execution mode, comprising:
Step S110: hydrolyzable titanium source is dissolved in ethanol, prepares hydrolyzable titanium source solution.
Wherein, in the present embodiment, hydrolyzable titanium source can be at least one in butyl titanate, tetraisopropyl titanate and titanium tetrachloride.Preferably, the titanium source of hydrolysis can be butyl titanate.
Preferably, in the solution of hydrolyzable titanium source, the mole of titanium elements and the volume ratio of ethanol are 0.5 ~ 1.5mol:1L.
Step S120: the nitrate of thulium is dissolved in the mixed solvent of water and ethanol, the solution of preparation containing thulium.
Wherein in an embodiment, containing in the solution of thulium, the concentration of the nitrate of thulium is 0.05 ~ 0.5mol/L.
Wherein in an embodiment, the nitrate of thulium is one or more in yttrium nitrate, lanthanum nitrate and cerous nitrate.
Wherein in an embodiment, in the mixed solvent of water and ethanol, the volume ratio of water and ethanol is 1:1 ~ 1:5.
Wherein in an embodiment, also comprise step: regulate the acid-base value of the solution containing thulium to be less than or equal to 5 to pH, be conducive to the carrying out of thulium stable and sequential hydrolysis reaction in the solution.Preferably, the acid that adjust ph is used is one or more in nitric acid, hydrochloric acid, sulfuric acid and glacial acetic acid.
Step S130: hydrolysis is occurred for hydrolyzable titanium source solution and the mixing of the solution containing thulium, prepares rear-earth-doped titania colloidal solate.
In the present embodiment, in rear-earth-doped titania colloidal solate, the mol ratio of titanium elements and thulium controls in 100:0.1 ~ 10.
Step S140: rear-earth-doped titania colloidal solate is coated on porcelain insulator surface, heat-treats after drying, obtains the porcelain insulator of surface modification.
Wherein in an embodiment, rear-earth-doped titania colloidal solate is coated on porcelain insulator surface and adopts brushing method or spraying process, rear-earth-doped titania colloidal solate is coated on porcelain insulator surface equably, forms one deck continuous uniform and transparent dissolved glue film.
Wherein in an embodiment, rear-earth-doped titania colloidal solate is 1 ~ 10mL/m at the coated weight of porcelain insulator surface
2.
Wherein in an embodiment, dry condition is dry 5 ~ 30min at 50 ~ 80 DEG C, and heat treated condition is in 350 ~ 650 DEG C of process 2 ~ 6h.Obtain the rear-earth-doped titanium dioxide base film of one deck continuous uniform at porcelain insulator surface after heat treatment.
Wherein in an embodiment, the thickness of rear-earth-doped titanium dioxide base film is 100 ~ 500nm.
Be appreciated that step S110 or step S120 can omit, directly hydrolyzable titanium source mixed with the solution containing thulium and hydrolysis occurs, prepare rear-earth-doped titania colloidal solate.
The preparation method of the porcelain insulator of above-mentioned surface modification, the rear-earth-doped titanium deoxid film of one deck is applied at porcelain insulator surface, the Superhydrophilic of titanium deoxid film and photocatalytic activity make film surface keep automatically cleaning and easy cleaning for a long time, reach the effect the generation reducing pollution flashover accident that reduce filthy accumulation, the rear-earth-doped photocatalysis efficiency that improve titanium deoxid film, solve titanium deoxid film and only under UV-irradiation, just have photocatalysis effect, and the accounting of ultraviolet light in sunlight is less than the problem of 5%, thus the anti-contamination performance of porcelain insulator surface is improved, electric property also makes moderate progress, fundamentally reduce the pollution flashover phenomenon that surperficial contamination causes.In addition, preparation method's technique of the porcelain insulator of above-mentioned surface modification is simple, and easy to operate, cost is low, and the porcelain insulator long service life of the surface modification obtained, has actual application prospect widely.
The preparation method of the porcelain insulator of above-mentioned surface modification, essence is by changing light-catalyzed reaction process to the modification of titanium dioxide, promote the migration in light induced electron and hole, make the time lengthening that they are separated, suppress the compound in electronics and hole, thus improve the photocatalysis efficiency of titanium dioxide, porcelain insulator surface is made to have light self cleaning function, greatly reduce the filth accumulation degree of porcelain insulator out of doors under service condition, improve electric property simultaneously, fundamentally reduce the pollution flashover phenomenon that surperficial contamination causes.
The preparation method of the porcelain insulator of above-mentioned surface modification, is applicable to the circuit porcelain insulator of different size and the surface treatment of pillar porcelain insulator, thus obtains that this cost is low, the porcelain insulator of the antifouling work of long service life.
In addition, present embodiment additionally provides a kind of porcelain insulator of surface modification, and the porcelain insulator of this surface modification adopts the preparation method of the porcelain insulator of above-mentioned surface modification to obtain.
The porcelain insulator of above-mentioned surface modification is by applying the rear-earth-doped titanium deoxid film of one deck at porcelain insulator surface, the Superhydrophilic of titanium deoxid film and photocatalytic activity make film surface keep automatically cleaning and easy cleaning for a long time, reach the effect the generation reducing pollution flashover accident that reduce filthy accumulation, the rear-earth-doped photocatalysis efficiency that improve titanium deoxid film, solve titanium deoxid film and only under UV-irradiation, just have photocatalysis effect, and the accounting of ultraviolet light in sunlight is less than the problem of 5%, thus the anti-contamination performance of porcelain insulator surface is improved, electric property also makes moderate progress, fundamentally reduce the pollution flashover phenomenon that surperficial contamination causes.The porcelain insulator cost of above-mentioned surface modification is low, long service life, have actual application prospect widely.
It is below specific embodiment.
Embodiment 1
Butyl titanate is joined in ethanol in the ratio that titanium elements and ethanol are 0.5mol:1L, mix and blend 30min, prepare hydrolyzable titanium source solution.
Be the ratio mixing of 1:1 by volume by water and ethanol, be the yttrium nitrate solution that 100:0.1 slowly adds 0.5mol/L by the mol ratio of the titanium elements in hydrolyzable titanium source and thulium, its pH to 4.5 is regulated, the solution of preparation containing thulium with nitric acid.
Under agitation hydrolyzable titanium source solution and the solution containing thulium are slowly mixed, form rare earth Yt doped titania colloidal solate.
Brushing method is adopted rare earth Yt doped titania colloidal solate to be coated on the porcelain insulator surface film forming that model is C4-80.Dry 30min at 50 DEG C, then heat-treats 4h at 450 DEG C, obtains the porcelain insulator of surface modification.
Embodiment 2
Tetraisopropyl titanate is joined in ethanol in the ratio that titanium elements and ethanol are 1.5mol:1L, mix and blend 60min, prepare hydrolyzable titanium source solution.
Be the ratio mixing of 1:3 by volume by water and ethanol, be the yttrium nitrate solution that 100:5 slowly adds 0.05mol/L by the mol ratio of the titanium elements in hydrolyzable titanium source and thulium, its pH to 5.0 is regulated, the solution of preparation containing thulium with nitric acid.
Under agitation hydrolyzable titanium source solution and the solution containing thulium are slowly mixed, form rare earth Yt doped titania colloidal solate.
Brushing method is adopted rare earth Yt doped titania colloidal solate to be coated on the porcelain insulator surface film forming that model is C4-80.Dry 5min at 80 DEG C, then heat-treats 2h at 350 DEG C, obtains the porcelain insulator of surface modification.
Embodiment 3
Butyl titanate is joined in ethanol in the ratio that titanium elements and ethanol are 1.0mol:1L, mix and blend 40min, prepare hydrolyzable titanium source solution.
Be the ratio mixing of 1:5 by volume by water and ethanol, be the yttrium nitrate solution that 100:10 slowly adds 0.2mol/L by the mol ratio of the titanium elements in hydrolyzable titanium source and thulium, its pH to 1.2 is regulated, the solution of preparation containing thulium with nitric acid.
Under agitation hydrolyzable titanium source solution and the solution containing thulium are slowly mixed, form rare earth Yt doped titania colloidal solate.
Brushing method is adopted rare earth Yt doped titania colloidal solate to be coated on the porcelain insulator surface film forming that model is C4-80.Dry 15min at 60 DEG C, then heat-treats 6h at 650 DEG C, obtains the porcelain insulator of surface modification.
Comparative example 1
Comparative example 1 is with the difference of embodiment 1, by the solution containing thulium in embodiment 1, replace with the solution not containing thulium, concrete, be the ratio mixing of 1:1 by volume by water and ethanol, obtain the solution not containing thulium.Other steps are all identical, obtain plating titanium dioxide film porcelain film insulator.
Comparative example 2
Uncoated common insulator, model be C4-80 porcelain insulator.
Performance test 1
The porcelain insulator that embodiment 1, comparative example 1, comparative example 2 obtain is respectively used to photocatalysis effect experiment, to analyze the anti-fouling flashover performance of porcelain insulator.Concrete grammar is as follows:
Using methyl orange as simulation organic pollution, by ultraviolet-visible spectrophotometer monitoring sample surfaces with the situation of change of light application time, evaluate the anti-fouling flashover performance of porcelain insulator.Accurately take a certain amount of methyl orange methyl orange aqueous solution being mixed with 25mg/L soluble in water.The porcelain insulator that embodiment 1, comparative example 1, comparative example 2 obtain is divided into three groups, often group gets three Duplicate Samples, drop into respectively in the methyl orange aqueous solution of 25mg/L, after adsorption equilibrium 30min, open uv light irradiation 6h, then sample about 3.0mL, measure the change of the ultraviolet-visible absorption spectroscopy of solution with ultraviolet-visual spectrometer, and evaluate the anti-fouling flashover performance of porcelain insulator with the rate of change of absorbance and degradation rate.The experimental result obtained is as shown in table 1.
Table 1
| Group | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| Degradation rate | 95～100％ | 47～55％ | 0％ |
Experimental result shows, the degradation rate of embodiment 1 and comparative example's 1 pair of methyl orange simulation organic pollution is respectively 95 ~ 100% and 47 ~ 55%, and the methyl orange of comparative example 2 simulation organic pollution is substantially without degraded.As can be seen here, the surface that embodiment 1 obtains has the porcelain insulator of rare earth modified titanium deoxid film, there is excellent degradable organic pollutant performance under illumination condition, its degradation rate is about 2 times of the not rare earth doped titanium deoxid film of comparative example 2, illustrates that it has excellent antifouling work effect.
Performance test 2
The porcelain insulator that embodiment 1, comparative example 1, comparative example 2 obtain is respectively used to anti-contamination performance test, to analyze the anti-fouling flashover performance of porcelain insulator.Concrete employing the following two kinds method is tested respectively:
A, conventional outdoor placement.Porcelain insulator embodiment 1, comparative example 1, comparative example 2 obtained respectively routine is placed on open air, within 15 days, observes the anti-pollution characteristic on its surface afterwards.The porcelain insulator surface of embodiment 1 has almost no change, totally as before; The porcelain insulator surface of comparative example 1 is then stained with tiny particle dust, and color is relatively dark; And the porcelain insulator surface of comparative example 2 is stained with a large amount of fine particle dust things, color is more gloomy.
B, manual simulation's contamination are tested.Comprise the organic dunghill experiment of simulation and simulate the experiment of inorganic dunghill.
Simulate organic dunghill real.Adopt oil with common edible as the organic dunghill of simulation, the process of coating edible oil is: be first dissolved in by the edible oil of 10mL in the acetone of 80mL and dilute, the porcelain insulator surface that the oleic acid after dilution is sprayed at embodiment 1 by recycling sprayer respectively equably, comparative example 1, comparative example 2 obtain.Simulate filthy liquid to be then made up of kaolin and NaCl.The time unification of outdoor placement is 15 days.
Simulate the experiment of inorganic dunghill.It is soft that kaolin has matter, and easy dispersion suspension, can as the analogies of floating dust in water and the feature such as high-adhesion; NaCl is then the soluble salt composition in simulation pollution layer.Be that the water of 200:10:1, kaolin and NaCl are mixed with and simulate inorganic dunghill by mass ratio, inorganic dunghill will be simulated load in water sprager, be sprayed at embodiment 1 respectively equably, porcelain insulator that comparative example 1, comparative example 2 obtain manually defile.The time unification of outdoor placement is 15 days.
The evaluation of pollution severity of insulators degree: pollution severity of insulators degree is measured according to State Grid Corporation of China's standard " level and external insulation choice criteria are distinguished in Q/GDW152-2006 electric power system dirt ".Pollution severity of insulators degree situation is evaluated with equivalent salt density ESDD value and the close NSDD value of ash.The experimental result obtained is as shown in table 2.Wherein, the unit of ESDD value and NSDD value is mg/cm
2.
Table 2
Experimental result shows, the surface that embodiment 1 obtains has the porcelain insulator of rare earth modified titanium deoxid film, and its equivalent salt density ESDD value and the close NSDD value of ash are all better than comparative example 1 and comparative example 2.As can be seen here, the surface that embodiment 1 obtains has the porcelain insulator of rare earth modified titanium deoxid film, and anti-contamination performance is good, illustrates that it has excellent antifouling work effect.
Comprehensive two kinds of method test results, illustrate after porcelain insulator surface plates rare earth modified titanium deoxid film, show good anti-contamination accumulation characteristics, improve the antifouling work effect of porcelain insulator.
The result of all-round property testing 1 and performance test 2, illustrates after porcelain insulator surface plates rare earth modified titanium deoxid film, shows good PhotoelectrocatalytiPerformance Performance and good anti-contamination accumulation characteristics, illustrates that it has excellent antifouling work effect thus.
Performance test 3
The porcelain insulator that embodiment 1, comparative example 1, comparative example 2 obtain is carried out electric performance test respectively, and often group gets three Duplicate Samples.Electric performance test is undertaken by GB/T775.2-2003, and pilot project is thunder and lightning all-wave impact dry flashover/wet flash-over voltage test, and the experimental result obtained is as shown in table 3.
Table 3
Experimental result shows, the porcelain insulator obtained from mean value embodiment 1 compares with comparative example 1, and dry flashover voltage slightly improves, and wet flash-over voltage is significantly improved, and this illustrates that the electric property of the porcelain insulator that embodiment 1 obtains also has greatly improved.
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be the scope that this specification is recorded.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for the porcelain insulator of surface modification, is characterized in that, comprises the steps:
, there is hydrolysis by hydrolyzable titanium source and the mixing of the solution containing thulium, prepare rear-earth-doped titania colloidal solate in step one;
Step 2, is coated on porcelain insulator surface by described rear-earth-doped titania colloidal solate, heat-treats after drying, obtain the porcelain insulator of described surface modification.
2. the preparation method of the porcelain insulator of surface modification according to claim 1, is characterized in that,
In described hydrolyzable titanium source, solute is at least one in butyl titanate, tetraisopropyl titanate and titanium tetrachloride, and solvent is ethanol.
3. the preparation method of the porcelain insulator of surface modification according to claim 2, is characterized in that, in described hydrolyzable titanium source, the mole of titanium elements and the volume ratio of ethanol are 0.5 ~ 1.5mol:1L.
4. the preparation method of the porcelain insulator of surface modification according to claim 1, is characterized in that, in described rear-earth-doped titania colloidal solate, the mol ratio of titanium elements and thulium is 100:0.1 ~ 10.
5. the preparation method of the porcelain insulator of surface modification according to claim 1, is characterized in that, described containing in the solution of thulium, solute is the nitrate of thulium, and solvent is the mixed solvent of water and ethanol.
6. the preparation method of the porcelain insulator of surface modification according to claim 5, is characterized in that, the nitrate of described thulium is one or more in yttrium nitrate, lanthanum nitrate and cerous nitrate; In the mixed solvent of described water and ethanol, the volume ratio of water and ethanol is 1:1 ~ 1:5.
7. the preparation method of the porcelain insulator of surface modification according to claim 5, is characterized in that, before described step one, also comprise step: regulate the acid-base value of the described solution containing thulium to be less than or equal to 5 to pH.
8. the preparation method of the porcelain insulator of surface modification according to claim 1, is characterized in that, described rear-earth-doped titania colloidal solate is 1 ~ 10mL/m at the coated weight of porcelain insulator surface
2.
9. the preparation method of the porcelain insulator of surface modification according to claim 1, is characterized in that, the condition of described drying is dry 5 ~ 30min at 50 ~ 80 DEG C, and described heat treated condition is in 350 ~ 650 DEG C of process 2 ~ 6h.
10. a porcelain insulator for surface modification, is characterized in that, adopts the preparation method of the porcelain insulator of the surface modification described in claim 1 ~ 9 any one to obtain.
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| CN109061404A (en) * | 2018-06-25 | 2018-12-21 | 国网湖南省电力有限公司 | Internal clearance lightning arrester discharge pipe is along face ablation test device and test method |
| CN116425515A (en) * | 2023-04-24 | 2023-07-14 | 江西省怡龙电气有限公司 | Toughening rod type porcelain insulator and preparation method thereof |
| CN117253682A (en) * | 2023-09-11 | 2023-12-19 | 连云港石港高压电瓷有限公司 | Disk-shaped cementing suspension porcelain insulator |
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