CN111037819A - A preparation method of epoxy insulating composite material with improved static dissipative properties - Google Patents
A preparation method of epoxy insulating composite material with improved static dissipative properties Download PDFInfo
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- CN111037819A CN111037819A CN201911059425.9A CN201911059425A CN111037819A CN 111037819 A CN111037819 A CN 111037819A CN 201911059425 A CN201911059425 A CN 201911059425A CN 111037819 A CN111037819 A CN 111037819A
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000004593 Epoxy Substances 0.000 title claims abstract description 26
- 230000003068 static effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 57
- 239000011737 fluorine Substances 0.000 claims abstract description 57
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000006082 mold release agent Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 239000007921 spray Substances 0.000 claims abstract description 12
- 238000005070 sampling Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 81
- 238000009413 insulation Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 6
- 239000011810 insulating material Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002918 waste heat Substances 0.000 claims description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012212 insulator Substances 0.000 abstract description 13
- 238000009825 accumulation Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 239000000523 sample Substances 0.000 description 30
- 239000010410 layer Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 7
- 229910018503 SF6 Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
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- 238000003682 fluorination reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 3
- 229960000909 sulfur hexafluoride Drugs 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000005516 deep trap Effects 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/22—Component parts, details or accessories; Auxiliary operations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
本发明提供了一种改善静电消散特性的环氧绝缘复合材料制备方法，属于环氧绝缘子技术领域，包括将含氟脱模剂均匀喷涂在模具内表面，放入干燥箱中烘烤干燥，形成致密脱模剂膜层；取出后，在致密脱模剂膜层外再次喷涂脱模剂，形成二次脱模剂膜层；将环氧树脂混合料浇注至形成脱模剂膜层的模具内，静置一定时间，待浇注产生的气泡排尽；将浇注环氧树脂混合料的模具放入干燥箱内，按照温度梯度进行固化，冷却至室温脱模取样，得到静电消散性能改善的环氧绝缘子。本发明将含氟成分引入了环氧复合体系中，采用二次喷涂含氟脱模剂的预处理工序，形成含氟渗透层，减少了环氧树脂的静电电荷积聚，提高了环氧树脂表面的静电消散速度，操作简单方便，成本低。
The invention provides a method for preparing an epoxy insulating composite material with improved static dissipative properties, belonging to the technical field of epoxy insulators. Dense mold release agent film layer; after taking out, spray mold release agent outside the dense mold release agent film layer again to form a secondary mold release agent film layer; pour the epoxy resin mixture into the mold forming the mold release agent film layer , let stand for a certain period of time until the bubbles generated by pouring are exhausted; put the mold for pouring the epoxy resin mixture into a drying box, solidify according to the temperature gradient, cool to room temperature and demould for sampling to obtain an epoxy resin with improved static dissipative properties insulator. The invention introduces the fluorine-containing component into the epoxy composite system, adopts the pretreatment process of secondary spraying of the fluorine-containing mold release agent to form a fluorine-containing permeable layer, reduces the electrostatic charge accumulation of the epoxy resin, and improves the surface of the epoxy resin. Fast static dissipation speed, simple and convenient operation and low cost.
Description
Technical Field
The invention relates to the technical field of epoxy insulators, in particular to a preparation method of an epoxy insulating composite material capable of reducing electrostatic charge accumulation of epoxy resin, improving the electrostatic dissipation speed of the surface of the epoxy resin and improving the electrostatic dissipation characteristic.
Background
The power transmission lines in China often pass through areas with complex geographical and meteorological conditions, and the selection of line corridors becomes an increasingly serious problem due to the development of social economy. The gas insulated metal enclosed transmission line (GIL) has the advantages of large transmission capacity, flexible arrangement, small mutual influence with the environment, no influence by external environmental factors such as dust, humidity and ice coating and the like, and is suitable for power transmission occasions with severe meteorological environments or restricted corridor selection.
In the direct current GIL, the epoxy resin basin-type insulator works under severe working conditions of strong electric field, large current, high temperature and high pressure for a long time, surface charges are accumulated on the surface of the epoxy resin basin-type insulator due to the continuous action of multiple fields, so that an electric field at an accumulation part is distorted, and surface flashover is induced. In view of this problem, researchers have proposed many modification ideas, among which fluorination treatment is an effective modification method. The fluorine-containing component is adopted to perform fluorination treatment on the surfaces of the filler, the matrix or the finished product in the epoxy composite system, so that the charge transport property of the epoxy composite system can be effectively improved, the dissipation rate of electrostatic charges on the surface of an insulator is accelerated, the unevenness of an electric field along the surface of the insulator is reduced, and the flashover trigger voltage is improved. The fluorination technology is various, but the prior method is independent of the production process of the insulator and is difficult to effectively put into industrial application on the premise of not adding novel production equipment.
Disclosure of Invention
The invention aims to provide a preparation method of an epoxy insulating composite material for reducing electrostatic charge accumulation of epoxy resin, improving electrostatic dissipation speed on the surface of the epoxy resin and improving electrostatic dissipation characteristics, so as to solve the technical problems in the background technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of an epoxy insulating composite material with improved static dissipation characteristics, which comprises the following steps:
step S110: cleaning the inner surface and the outer surface of a mold, uniformly spraying a fluorine-containing release agent on the inner surface of a stainless steel mold, putting the mold into a drying oven for baking and drying, and forming a compact release agent film layer on the inner surface of the mold;
step S120: after the mold is taken out of the drying box, spraying the fluorine-containing release agent again outside the compact release agent film layer, and forming a secondary release agent film layer by utilizing waste heat;
step S130: pouring the epoxy resin mixture into a mold for forming a mold release agent film layer, standing for a certain time, and discharging bubbles generated by pouring;
step S140: and placing the mold for pouring the epoxy resin mixture into a drying oven, curing according to a certain temperature gradient, naturally cooling to room temperature, demolding and sampling to obtain the epoxy insulator with improved static dissipation performance.
Preferably, in step S130, bisphenol A epoxy resin monomer, methyl tetrahydrophthalic anhydride curing agent, accelerator, spherical 50 mesh modified micron Al are respectively taken2O3And (4) uniformly mixing, and stirring and degassing in vacuum to obtain the epoxy resin mixture.
Preferably, bisphenol A epoxy resin monomer, methyl tetrahydrophthalic anhydride curing agent, accelerator and spherical 50-mesh modified micron Al2O3The mass ratio of (A) to (B) is 100:85:0.5: 330.
Preferably, the accelerator is 2, 4, 6-tris (dimethylaminomethyl) phenol.
Preferably, the fluorine-containing release agent comprises ultra-small molecular weight polytetrafluoroethylene, the molecular weight of the ultra-small molecular weight polytetrafluoroethylene is 500-5000, and the total mass of the fluorine-containing release agent of the ultra-small molecular weight polytetrafluoroethylene station is 20-40%.
Preferably, an air pump spray gun carrying the fluorine-containing release agent is adopted to uniformly spray the fluorine-containing release agent on the inner surface of the stainless steel mold at the speed of 0.1mL/s, and the spraying amount is 0.005-0.015mL/cm2。
Preferably, the mold is placed into a drying oven and baked for 10 hours at 140 ℃ to form a compact release agent film layer.
Preferably, the vacuum stirring and degassing is to maintain the stirring at 60 ℃ for 30 hours in a vacuum environment, and to completely remove air bubbles in the mixture.
Preferably, the epoxy resin mixture is poured into a mold for forming a release agent film layer and stands for 5 min.
Preferably, curing according to a temperature gradient comprises curing at 140 ℃ for 2h, followed by curing at 160 ℃ for 10 h.
The invention has the beneficial effects that: the method introduces fluorine-containing components into an epoxy composite system by a soft and efficient method, improves the coating process of the release agent, adopts a pretreatment process of spraying the fluorine-containing release agent for the second time, effectively forms a fluorine-containing permeable layer on the surface of the composite material, reduces the electrostatic charge accumulation of the epoxy resin, improves the electrostatic dissipation speed on the surface of the epoxy resin, overcomes the defect of a short plate of the basin-type insulator material which is easy to accumulate surface charges, and has the advantages of simple operation, convenient implementation, low cost and strong industrial applicability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flow chart of a method for preparing an epoxy insulation composite material with improved static dissipation characteristics according to an embodiment of the present invention.
FIG. 2 is a schematic representation of the surface microstructure of a silicon-containing mold release agent according to an embodiment of the present invention.
FIG. 3 is a graph showing the distribution of silicon content of the silicon-containing release agent in different depths in the composite material according to the embodiment of the present invention.
FIG. 4 is a schematic view of the surface microstructure of a fluorine-containing mold release agent according to an embodiment of the present invention.
FIG. 5 is a graph showing the distribution of fluorine content in the composite material at different depths in the fluorine-containing mold release agent according to the embodiment of the present invention.
Fig. 6 is a schematic diagram of a monitoring and charging device for a sample surface charge test according to an embodiment of the present invention.
FIG. 7 is a graph showing the results of a two-dimensional test of surface charge accumulation for four samples according to an embodiment of the present invention.
Fig. 8 is a graphical illustration of a normalized plot of the surface potential decay during dissipation of an insulating material in accordance with an embodiment of the present invention.
Fig. 9 is a schematic diagram of a potential trap distribution result calculated by an isothermal surface potential decay method according to an embodiment of the present invention.
Fig. 10 is a diagram illustrating the resistivity test result of the insulating material according to the embodiment of the invention.
Fig. 11 is a schematic diagram illustrating a surface flashover voltage test result after the dc pre-pressing of the insulating material according to the embodiment of the invention.
Detailed Description
The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or modules, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, modules, and/or groups thereof.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For the convenience of understanding of the embodiments of the present invention, the following description will be further explained by taking specific embodiments as examples with reference to the drawings, and the embodiments are not to be construed as limiting the embodiments of the present invention.
It will be understood by those of ordinary skill in the art that the figures are merely schematic representations of one embodiment and that the elements or devices in the figures are not necessarily required to practice the present invention.
Examples
As shown in fig. 1, an embodiment of the present invention provides a method for preparing an epoxy insulation composite material with improved static dissipation characteristics, which includes the following steps:
step S110: cleaning the inner surface and the outer surface of a mold, uniformly spraying a fluorine-containing release agent on the inner surface of a stainless steel mold, putting the mold into a drying oven for baking and drying, and forming a compact release agent film layer on the inner surface of the mold;
step S120: after the mold is taken out of the drying box, spraying the fluorine-containing release agent again outside the compact release agent film layer, and forming a secondary release agent film layer by utilizing waste heat;
step S130: pouring the epoxy resin mixture into a mold for forming a mold release agent film layer, standing for a certain time, and discharging bubbles generated by pouring;
step S140: and placing the mold for pouring the epoxy resin mixture into a drying oven, curing according to a certain temperature gradient, naturally cooling to room temperature, demolding and sampling to obtain the epoxy insulator with improved static dissipation performance.
In step S130, bisphenol A epoxy resin monomer, methyl tetrahydrophthalic anhydride curing agent, accelerator and spherical 50-mesh modified micron Al are respectively taken2O3And (4) uniformly mixing, and stirring and degassing in vacuum to obtain the epoxy resin mixture.
Bisphenol A epoxy resin monomer, methyl tetrahydrophthalic anhydride curing agent, accelerator and spherical 50-mesh modified micron Al2O3The mass ratio of (A) to (B) is 100:85:0.5: 330. Wherein the accelerant is 2, 4, 6-tris (dimethylaminomethyl) phenol.
The fluorine-containing release agent comprises ultra-small molecular weight polytetrafluoroethylene, the molecular weight of the ultra-small molecular weight polytetrafluoroethylene is 500-5000, and the total mass of the fluorine-containing release agent of the ultra-small molecular weight polytetrafluoroethylene station is 20-40%.
Adopting an air pump spray gun carrying the fluorine-containing release agent to uniformly spray the fluorine-containing release agent on the inner surface of the stainless steel die at the speed of 0.1mL/s, wherein the spraying amount is 0.005-0.015mL/cm2。
And (3) placing the die into a drying oven, and baking for 10 hours at 140 ℃ to form a compact release agent film layer.
The vacuum stirring and degassing is to keep stirring for 30 hours at 60 ℃ in a vacuum environment, and to completely remove air bubbles in the mixture.
And pouring the epoxy resin mixture into a mold for forming a release agent film layer, and standing for 5 min.
Curing according to a certain temperature gradient comprises curing at 140 ℃ for 2h, and then curing at 160 ℃ for 10 h.
Comparative test experiment
Preparation of insulating material
Step (1): cleaning the surface of the mold, uniformly spraying the mold release agent on the inner surface of the stainless steel mold at the speed of 0.1mL/s by using an air pump spray gun loaded with the mold release agent, and then putting the mold into a drying oven at the temperature of 140 ℃ for baking for 10 hours to form a compact mold release agent film layer.
And taking out the mold from the drying box, spraying the mold release agent on the compact mold release agent film layer again, and forming a second mold release agent film layer by utilizing the waste heat of the mold.
Step (2): simultaneously with the step (1), taking bisphenol A type epoxy resin monomer, methyl tetrahydrophthalic anhydride curing agent, accelerant and spherical 50-mesh modified micron Al2O3The ratio of 100:85:0.5:330, stirring for 30 hours at the temperature of 60 ℃ in a vacuum environment, slowly pouring the mixture into a mold with two layers of mold release agent films after air bubbles in the mixture are completely removed.
And (3): and standing for 5min after the mold is filled, removing a small amount of bubbles generated by casting after heating, then putting the mold into a drying oven at 140 ℃ for curing for 2h, curing for 10h at 160 ℃, naturally cooling to room temperature after completion, demolding and sampling.
In the test, two release agents, i.e., a silicon release agent and a fluorine release agent, were used, and four kinds of sample pieces were prepared in total in accordance with the respective spraying amounts (spraying amount 0.01 mL/cm)2) Sample 1 of a fluorine-based mold release agent (spray amount: 0.005 mL/cm)2) Fluorine-based mold release agent sample 2 (spray amount 0.01 mL/cm)2) And fluorine-based mold release agent sample 3 (spray amount of 0.015 mL/cm)2) And are labeled in the following description and test drawings.
The main component of the fluorine-containing release agent is ultra-small molecular weight polytetrafluoroethylene, the molecular weight is 500-5000, and the fluorine-containing release agent accounts for 20-40% of the total mass of the release agent, and the fluorine-containing release agent and the volatile dissolving auxiliary agent are mixed to prepare a finished product reagent.
As shown in FIG. 2, by the above-described operation, an epoxy composite sample sheet with an impregnation layer using a silicon-based release agent was obtained, and the effect of the impregnation layer is partially illustrated in FIG. 3.
As shown in fig. 2, it was found that the silicon-based mold release composite did not show much difference in morphology between the infiltrated layer and the components in the matrix. FIG. 3 is a graph of Si content distribution with depth of penetration. It was found that the Si content in the surface layer was about 2.96% by mass and the Si content in the depth of 200 μm was reduced to about 0.71%. Fig. 4 to 5 show the test results of the fluorine-containing mold release agent sample 2, and it can be found that the fluorine mass ratio of the composite material surface layer reaches 5.45% under the same preparation flow and is reduced to nearly zero value at 200 μm after the fluorine-containing mold release agent is adopted. In conclusion, after the fluorine-containing release agent is used for replacing a silicon-containing release agent, the residual amount of the characteristic groups of the fluorine-containing release agent is improved, and meanwhile, the depth of a permeable layer is close to 200 mu m and is slightly changed.
As shown in fig. 6, a schematic diagram of a monitoring and charging device used for surface charge testing is shown, in the testing process, a sample wafer is firstly clamped between two probe electrodes with a distance of 10mm, a length of 10mm and a tip curvature radius of 5 μm, 10kV direct-current positive polarity voltage is applied to one side electrode, the other side electrode is grounded, a very uneven tangential electric field is formed, and then the surface of the sample is charged, so as to simulate charge accumulation of a material under a severe working condition.
Charging lasts for 1min, then moving the sample to a position 2mm below the Kelvin probe through a sliding rail, measuring the potential of a charged area on the upper surface of the sample at a block speed through a stepping two-dimensional guide rail where the Kelvin probe is located, wherein the measured area is a square with the size of 20mm multiplied by 20mm, after scanning, taking a point on a gap 1.5mm away from the side of the high-voltage electrode to monitor the potential, and the subsequent monitoring time is 2000 s.
As shown in fig. 7, the surface charge accumulation two-dimensional test results for the four samples are shown schematically. Fig. 7(a), 7(b), 7(c), and 7(d) show the results of the two-dimensional surface charge accumulation test after charging for 1min for the silicon release agent sample, the fluorine release agent sample 1, the fluorine release agent sample 2, and the fluorine release agent sample 3, respectively. It was found that when the silicon-based release agent was replaced with the fluorine-containing release agent, the charge potential on the upper surface of the sample piece increased, and the amount of the release agent increased from 5100V to 5600V, which was 9.8%. Meanwhile, when a silicon-based release agent was used, the potential distribution on the material surface was concentrated, and when the release agent was replaced with a fluorine-containing release agent, the area of the high potential region on the surface was increased, and the material tended to diffuse in the direction perpendicular to the gap direction (Y direction). This shows that with the fluorine-containing release agent, the response capability of the material to surface charges is enhanced, the dissipation area of the surface charges in a limited time is increased, and the uniformity of the overall charge distribution is increased.
As shown in FIG. 8, in order to normalize the curve of the surface potential decay during dissipation, it was found that the silicon-based mold release agent was usedAfter the fluorine-containing release agent is replaced, the surface charge dissipation rate is enhanced and can be increased to about 840 percent of the original maximum rate. Meanwhile, according to the trap distribution result calculated by the isothermal surface potential attenuation method in fig. 9, it can be found that the traps of the composite material prepared by the silicon release agent are mainly deep traps, the corresponding energy level depth is 1.084eV, and the peak height is 1427 × 1019eV-1·m3After the fluorine-containing release agent is adopted, the deep trap energy level and the intensity peak height of each sample are reduced, obvious shallow traps appear in the range of 0.95eV to 0.98eV, and the maximum shallow trap peak value can reach 441.7 multiplied by 1019eV-1·m3。
The shallow depth of the trap and the appearance of the shallow trap show that the fluorine-containing release agent improves the blocking capability of the composite material surface to charge transport and enhances the response capability to charge and electric field, which corresponds to the test result in fig. 9.
As shown in fig. 10, the surface resistivity of the composite material sample is measured by a three-electrode resistivity measurement method according to the relevant provisions of GB 1014-2006. The results show that the surface resistivity of the composite material using the silicon-containing release agent is 1017Omega, the surface resistivity is reduced by 1 to 2 orders of magnitude to 2.86 multiplied by 10 at most after the fluorine-containing release agent is adopted15Ω。
As shown in fig. 11, the test results of the creeping voltage of the material in air and sulfur hexafluoride are shown. Fig. 11(a) shows the test result of the surface flashover voltage of the composite material sample in the air, and fig. 11(b) shows the test result of the surface flashover voltage of the composite material sample in the sulfur hexafluoride.
The test electrode structure refers to the pin charging gap in fig. 8. Before testing, a direct current preset voltage is applied to the sample wafer for a certain time, the prepressing amplitude is 10kV, the prepressing time is 0 minute, 30 minutes, 60 minutes, 90 minutes and 120 minutes respectively, and after the prepressing is finished, the sample is subjected to flashover testing. During testing, the voltage is increased from 0, the average speed is controlled to be 0.1kV/s to 0.2kV/s, each sample wafer is tested for 10 times, an oscilloscope is used for connecting a voltage probe in series to measure the high-voltage terminal potential, and the average value and the standard deviation of the flashover voltage are taken for drawing and analyzing.
The result shows that the fluorine-containing release agent has a considerable modification effect when no prepressing exists in the flashover test in the air, the flashover voltage of the fluorine-containing release agent is increased to 16.2kV from 13.2kV of a silicon system to 22.7 percent, after prepressing, the flashover voltage of a silicon system sample piece is gradually reduced along with the prepressing time, is reduced to 12.3kV when the prepressing is carried out for 90min, and flashover occurs in the prepressing to 120 min. After the fluorine-containing release agent is adopted, the tendency of reduction of the flashover voltage of the material along with time is relieved, and for the sample 3, the flashover voltage is reduced to 16.1kV from 16.3kV only by pre-pressing for 120min, and is close to 1%. For SF6The same applies to the flashover voltage of the sample being SF6The effect of the insulation properties is multiplied, where the weakest point of the insulation along the surface is transferred to the solid phase of the composite material, under which the effect of the surface properties on flashover is amplified. It can be found that the flashover voltage of the silicon-based release agent is very large in normal price range along with the prepressing time, and the flashover voltage of the whole material shows a nearly constant trend along with the time after the fluorine-containing release agent is adopted.
In summary, the composite insulating material prepared by the epoxy insulating composite material preparation method for improving the static electricity dissipation characteristic is provided by the embodiment of the invention. The method is mainly focused on improving the mold release process, thereby affecting the surface composition, static dissipation characteristics and surface insulation properties of the cured product. Firstly, an air pump spray gun loaded with fluorine-containing release agent is adopted to uniformly spray the inner wall of a stainless steel mould, then the mould is placed in a drying box and heated at the temperature of 140-150 ℃ for 30min to form a film, then the mould in a high-temperature state is taken out, a release agent layer is sprayed on the formed compact film layer for the first time, and a secondary film layer is formed by means of the residual temperature of the mould. Meanwhile, according to the base material formula of the basin-type insulator for GIL, a bisphenol A epoxy resin monomer, a methyl tetrahydrophthalic anhydride curing agent, an accelerant and spherical 50-mesh modified micron Al2O3 are mixed according to the weight ratio of 100:85:0.5:330, shearing, stirring, vacuum degassing, pouring into a mold, and curing at a temperature gradient of 140 ℃/2h +160 ℃/10h in a vacuum environment. Test results prove that by adopting the pretreatment procedure of spraying the fluorine-containing release agent for the second time, a fluorine-containing permeable layer can be effectively formed on the surface of the composite material, and correspondingly, the charge dissipation capacity, the surface conductivity and the surface flashover voltage of the material in the environment of air and sulfur hexafluoride are improved. The method starts from a mold release process in the actual production of the insulator, is simple to implement and convenient to operate, and has strong industrial applicability.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of an epoxy insulation composite material with improved static dissipation characteristics is characterized by comprising the following steps:
step S110: cleaning the inner surface and the outer surface of a mold, uniformly spraying a fluorine-containing release agent on the inner surface of a stainless steel mold, putting the mold into a drying oven for baking and drying, and forming a compact release agent film layer on the inner surface of the mold;
step S120: after the mold is taken out of the drying box, spraying the fluorine-containing release agent again outside the compact release agent film layer, and forming a secondary release agent film layer by utilizing waste heat;
step S130: pouring the epoxy resin mixture into a mold for forming a mold release agent film layer, standing for a certain time, and discharging bubbles generated by pouring;
step S140: and placing the mold for pouring the epoxy resin mixture into a drying oven, curing according to a certain temperature gradient, naturally cooling to room temperature, demolding and sampling to obtain the epoxy insulating material with improved static dissipation performance.
2. The method of claim 1, wherein in step S130, the bisphenol A epoxy resin monomer, the methyl tetrahydrophthalic anhydride curing agent, and the accelerator are respectively selectedSpherical 50-mesh modified micron Al2O3And (4) uniformly mixing, and stirring and degassing in vacuum to obtain the epoxy resin mixture.
3. The method of claim 2, wherein the bisphenol A epoxy resin monomer, the methyl tetrahydrophthalic anhydride curing agent, the accelerator, and the spherical 50 mesh modified micron Al are used as the curing agent2O3The mass ratio of (A) to (B) is 100:85:0.5: 330.
4. The method for preparing the epoxy insulation composite material with improved static electricity dissipation characteristic as claimed in claim 3, wherein the fluorine-containing release agent comprises ultra-small molecular weight polytetrafluoroethylene, the molecular weight of the ultra-small molecular weight polytetrafluoroethylene is 500-5000, and the ultra-small molecular weight polytetrafluoroethylene is 20-40% of the total mass of the fluorine-containing release agent.
5. The method for preparing an epoxy insulation composite material with improved static electricity dissipation characteristics as claimed in claim 4, wherein the fluorine-containing release agent is uniformly sprayed onto the inner surface of the stainless steel mold at a rate of 0.1mL/s by using an air pump spray gun carrying the fluorine-containing release agent, and the spraying amount is 0.005-0.015mL/cm2。
6. The method for preparing an epoxy insulation composite material with improved static electricity dissipation characteristic as claimed in claim 5, wherein the mold is placed into a drying oven and baked for 10 hours at 140 ℃ to form a compact release agent film layer.
7. The method of preparing an epoxy insulation composite for improving static electricity dissipation characteristics as claimed in any one of claims 1 to 6, wherein the accelerator is 2, 4, 6-tris (dimethylaminomethyl) phenol.
8. The method for preparing an epoxy insulation composite material with improved static electricity dissipation characteristics as recited in any one of claims 1-6, wherein the vacuum stirring degassing is performed by stirring for 30 hours under a vacuum environment at 60 ℃, and air bubbles in the mixture are completely removed.
9. The method for preparing an epoxy insulation composite material with improved static electricity dissipation characteristics as claimed in claim 8, wherein the epoxy resin mixture is poured into the mold for forming the release agent film layer and left for 5 min.
10. The method of claim 9, wherein curing at a temperature gradient comprises curing at 140 ℃ for 2 hours followed by curing at 160 ℃ for 10 hours.
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