CN102585165A - Method for inhibiting accumulation of surface charge of epoxy resin and composite materials thereof - Google Patents
Method for inhibiting accumulation of surface charge of epoxy resin and composite materials thereof Download PDFInfo
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- CN102585165A CN102585165A CN2011104404886A CN201110440488A CN102585165A CN 102585165 A CN102585165 A CN 102585165A CN 2011104404886 A CN2011104404886 A CN 2011104404886A CN 201110440488 A CN201110440488 A CN 201110440488A CN 102585165 A CN102585165 A CN 102585165A
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Abstract
The invention belongs to the technical field of electrical insulating materials, and relates to an extremely effective method for inhibiting the accumulation of surface charge of epoxy resin and composite materials thereof. The method comprises the following step that the epoxy resin and the composite materials thereof are subject to gas phase fluorination treatment in a closed reaction chamber. The method disclosed by the invention is applied to the inhibition of the accumulation of the surface charge of electrical insulating pieces of the epoxy resin and the composite materials thereof, so as to improve the flashover voltages and the electrical insulating performance of the electrical insulating pieces, such as epoxy insulating supports and epoxy insulators of the epoxy resin and the composite materials thereof, and static electricity resistance of the epoxy resin and the composite materials thereof when the epoxy resin and the composite materials thereof are used in other aspects.
Description
Technical field
The invention belongs to the insulating material technical field, relate to a kind of very effective ways that suppress epoxy resin and the accumulation of composite material surface electric charge thereof.
Background technology
Epoxy resin-base composite material is owing to have remarkable electrical isolation, mechanics and thermal property and chemicalstability, has been widely used in fields such as electric, electronics and space flight and aviation.Especially the sulfur hexafluoride gas-insulating switching device (GIS) that supports with the epoxy resin-base composite material insulation; Because the structure of high insulating reliability, little floor space and sealing so that do not receive the influence etc. of external environment atmosphere, in high-voltage alternating (HVAC) electric power delivery system widespread use decades.As everyone knows, HVDC (HVDC) transmission of electricity has many advantages than the HVAC transmission of electricity, its develop fast press for match with it, can be at the corresponding switching device of safe and reliable application under the HVDC.Yet existing result of study and practical application have shown that manufacturing and designing the HVDC GIS that has with HVAC GIS same dielectric safety remains a challenge.Its major cause be compare with alternating-electric field, electric charge more is prone to accumulate on the surface that epoxy resins insulation supports under DC electric field, although under alternating-electric field, also there is the cumulative of electric charge usually.The too much serious distortion electric field of electric charge accumulation meeting of insulation stayed surface, cause declining to a great extent of edge flashing voltage, even cause that insulation is supported along face and puncture, cause equipment breakdown.Similarly surface charge accumulation problem also is present on epoxy insulation that uses under vacuum or the ambiance and some epoxide resin material tectums that use in others.Therefore, how to suppress under the highfield, especially under the direct current high field epoxy resins insulation support or insulator on the surface charge accumulation be one of problem of paying close attention to the most both at home and abroad for a long time.
Summary of the invention
The object of the present invention is to provide a kind of method that suppresses epoxy resin and the accumulation of composite material surface electric charge thereof, with insulating property and raising epoxy resin and the antistatic surface of matrix material when others are used thereof that improves epoxy resin and matrix material electric insulation spare thereof.
For reaching above purpose, the technical scheme that the present invention adopted is:
A kind of method that suppresses epoxy resin and the accumulation of composite material surface electric charge thereof comprises following steps: in airtight reaction chamber, epoxy resin and matrix material thereof are carried out the gas phase fluorination processing.
Described gas phase fluorination treatment temperature is a room temperature to 120 ℃, is preferably room temperature to 60 ℃.
The reactant gases that described gas phase fluorination is handled is fluorine gas/rare gas element gas mixture.
Described rare gas element is nitrogen or helium, nitrogen.
The volumetric concentration of fluorine gas is 1%-100% in described fluorine gas/rare gas element gas mixture, is preferably 5%-20%.
The reaction gas pressure that described gas phase fluorination is handled is 0.2-5bar, is preferably 0.2-1bar.
The described fluoridation time is 5min-120min, preferred 5min-60min.
Described epoxide resin material is the material of the resin adhesive liquid of glycidyl ether type, glycidyl ester type, glycidic amine type, alicyclic epoxide compound or wire aliphatic epoxy compound through corresponding curing process preparation, the solidify material of preferred bisphenol A diglycidyl ether resin.
Described epoxy resin composite material is the above-mentioned epoxy resin adhesive liquid and the material of the corresponding curing process preparation of strongthener (particulate state, fiber and textile material thereof) warp, preferred epoxy base silicon-dioxide or aluminium sesquioxide particulate composite and epoxy resin base glass fibre and Fabric composites thereof.
Described epoxy resin and matrix material thereof, they are applied to electric insulation spare (like epoxy insulation support and epoxy insulation etc.) or are employed the surface coating of making others, relating to the accumulation of static electricity problem.
Owing to adopted such scheme, the present invention to have following characteristics:
1. adopt that a kind of technology is simple, technology maturation, very effectively gas phase fluorination is handled, only change the chemical constitution and the structure of epoxy resin and composite layer thereof, and do not change its any body composition, structure and characteristic.
2. that adopts that the inventive method can obtain epoxy resin and the accumulation of composite material surface electric charge thereof suppresses effect very significantly, and electric charge can not be stored in fluoridizing in the top layer of epoxy resin and matrix material thereof.Depend on fluorination conditions and concrete epoxy resin and matrix material thereof, at room temperature in several minutes to tens minute, rapidly decay to zero even deposit to the electric charge that epoxy resin and matrix material thereof fluoridize on the top layer.
Description of drawings
Fig. 1 is the gas phase fluorination treatment system synoptic diagram of the inventive method epoxy resin and matrix material thereof.
Fig. 2 is the example through the epoxy resin of the inventive method gas phase fluorination processing and composite layer composition thereof.
Fig. 3 is the typical case of the epoxide resin material handled without the inventive method gas phase fluorination thermal stimulus discharge (TSD) current spectrum of opening a way.
Fig. 4 is the surface charge room temperature decay of embodiment of the invention 1-3 fluorinated epoxy resin sample.
Fig. 5 is the surface charge room temperature decay of embodiment of the invention 4-6 fluorinated epoxy resin sample.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is further described.
At first see also Fig. 1.Simple and the technology maturation of technological process of the inventive method and system.Only need the curing part of epoxy resin and matrix material thereof be placed and fluoridize the chamber, can under wide fluorination conditions illustrated in " summary of the invention ", carry out gas phase fluorination and handle (concrete fluorination conditions depends on the requirement of user to the fluorinated layer over-all properties).
See also Fig. 2.As everyone knows, the performance of material depends on its The Nomenclature Composition and Structure of Complexes.The inventive method is to the addition to two keys in their top layers of the replacement of the Wasserstoffatoms in epoxy resin and the composite layer thereof and other group and fluorine atom through fluorine atom; With chemical constitution and the structure (as shown in Figure 2) that changes their top layers, thus change the top layer electrology characteristic, reach the purpose of the top layer electric charge accumulation that suppresses them.
Compare with dark charge trap, the stable surface electric charge of handling without the inventive method (as shown in Figure 3) in epoxide resin material surface, can not stored charge on the surface of the epoxide resin material of employing the inventive method modification.Depend on fluorination conditions and concrete epoxy resin and matrix material thereof, at room temperature in several minutes to tens minute, rapidly decay to zero even deposit to the electric charge that epoxy resin and matrix material thereof fluoridize on the top layer.Therefore, this is to flash-over voltage and electrical insulation properties that improves epoxy resin and matrix material electric insulation spare thereof (supporting and epoxy insulation like epoxy insulation) and the antistatic surface property that improves epoxy resin and composite material overwrap thereof, and is very meaningful.
In order to carry out the comparison between embodiment, the thickness that employed sample is cured and prepared is about the identical epoxy resin sample of 0.55mm.Before surface potential or the surface charge decay of each embodiment of research, these embodiment samples press with grid voltage in pins and are respectively-10kV and-2kV, in atmosphere by corona charging 5min.It is 500V that their surface conductivity is measured according to GB MT113-1995 enforcement, measuring voltage.
Embodiment 1
In airtight reaction chamber, the epoxy resin sample being carried out gas phase fluorination handles.
The gas phase fluorination treatment condition: temperature is 50 ℃, and the volumetric concentration of fluorine gas is 12.5% in the delivery of fluorine/nitrogen gas mixture, and reaction gas pressure is 1bar, and the fluoridation time is 30min.
The measuring result of the decay of the surface potential of embodiment 1 sample or surface charge and surface conductivity: (stable initial surface current potential 2kV) is compared, and (2kV) and at room temperature surface potential or surface charge rapidly decay to zero (seeing also embodiment 1 curve among Fig. 4) to the initial surface current potential after the charging of embodiment 1 sample far below this charging grid voltage value with having the grid voltage of charging no better than behind sample (original sample) corona charging without fluoridation.The surface conductivity (11 * 10 of this and embodiment 1 sample
-13[S]) much larger than the surface conductivity (4.1 * 10 of original sample
-17[S]) measuring result consistent (seeing also table 1).
In airtight reaction chamber, the epoxy resin sample being carried out gas phase fluorination handles.
The gas phase fluorination treatment condition: temperature is 55 ℃, and the volumetric concentration of fluorine gas is 20% in the delivery of fluorine/nitrogen gas mixture, and reaction gas pressure is 0.2bar, and the fluoridation time is 60min.
The measuring result of the surface potential of embodiment 2 samples or surface charge decay and surface conductivity sees also embodiment 2 curve and the tables 1 among Fig. 4.Similar with the result of embodiment 1 sample; Also (2kV) and at room temperature surface potential or surface charge also rapidly decay to zero to the initial surface current potential of embodiment 2 samples after the charging, and the surface conductivity of embodiment 2 samples is also significantly greater than the surface conductivity of original sample far below charging grid voltage value.
Embodiment 3
In airtight reaction chamber, the epoxy resin sample being carried out gas phase fluorination handles.
The gas phase fluorination treatment condition: temperature is 120 ℃, and the volumetric concentration of fluorine gas is 1% in the delivery of fluorine/nitrogen gas mixture, and reaction gas pressure is 2bar, and the fluoridation time is 30min.
The measuring result of the surface potential of embodiment 3 samples or surface charge decay and surface conductivity sees also embodiment 3 curve and the tables 1 among Fig. 4.Similar with the result of embodiment 1 and 2 samples, but its surface potential or surface charge than the above two present quickly decay, because its higher surface conductivity (2.6 * 10
-13[S]).
Embodiment 4
In airtight reaction chamber, the epoxy resin sample being carried out gas phase fluorination handles.
The gas phase fluorination treatment condition: temperature is 40 ℃, and the volumetric concentration of fluorine gas is 1% in the delivery of fluorine/nitrogen gas mixture, and reaction gas pressure is 5bar, and the fluoridation time is 120min.
The measuring result of the surface potential of embodiment 4 samples or surface charge decay and surface conductivity sees also embodiment 4 curve and the tables 1 among Fig. 5.Similar with embodiment 1-3 sample, electric charge at room temperature can not be kept at the surface of embodiment 4 samples, owing to the surface conductivity that enlarges markedly than original sample.
In airtight reaction chamber, the epoxy resin sample being carried out gas phase fluorination handles.
The gas phase fluorination treatment condition: temperature is a room temperature, and the volumetric concentration of fluorine gas is 50% in the delivery of fluorine/nitrogen gas mixture, and reaction gas pressure is 0.2bar, and the fluoridation time is 15min.
The measuring result of the surface potential of embodiment 5 samples or surface charge decay and surface conductivity sees also embodiment 5 curve and the tables 1 among Fig. 5.Because the relative original sample of its surface conductivity has been increased nearly 5 one magnitude, surface charge is in decaying to zero under the room temperature, in 3 minutes rapidly.
In airtight reaction chamber, the epoxy resin sample being carried out gas phase fluorination handles.
The gas phase fluorination treatment condition: temperature is a room temperature, and the volumetric concentration of fluorine gas is 100% in the delivery of fluorine/nitrogen gas mixture, and reaction gas pressure is 0.2bar, and the fluoridation time is 5min.
The measuring result of the surface potential of embodiment 6 samples or surface charge decay and surface conductivity sees also embodiment 6 curve and the tables 1 among Fig. 5.The situation of measuring result and embodiment 5 samples is close.
Table 1
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (7)
1. method that suppresses the accumulation of epoxy resin and composite material surface electric charge thereof is characterized in that: comprise following steps:
In airtight reaction chamber, epoxy resin and matrix material thereof are carried out the gas phase fluorination processing.
2. method according to claim 1 is characterized in that: described gas phase fluorination treatment temperature is a room temperature to 120 ℃, preferred room temperature to 60 ℃.
3. method according to claim 1 is characterized in that: the reactant gases that described gas phase fluorination is handled is fluorine gas/rare gas element gas mixture.
4. method according to claim 3 is characterized in that: described rare gas element is nitrogen or helium, nitrogen.
5. method according to claim 3 is characterized in that: the volumetric concentration of fluorine gas is 1%-100% in described fluorine gas/rare gas element gas mixture, is preferably 5%-20%.
6. method according to claim 1 is characterized in that: the reaction gas pressure that described gas phase fluorination is handled is 0.2-5bar, preferred 0.2-1bar.
7. method according to claim 1 is characterized in that: the described fluoridation time is 5min-120min, preferred 5min-60min.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159975A (en) * | 2012-11-22 | 2013-06-19 | 天津学子电力设备科技有限公司 | Device enabling surface charge of polyimide film to dissipate rapidly |
| CN103205009A (en) * | 2012-11-21 | 2013-07-17 | 天津学子电力设备科技有限公司 | Preparation method of corona resistant polyimide film having three-layer structure |
| CN103280280A (en) * | 2013-04-25 | 2013-09-04 | 西北核技术研究所 | Method for improving flashover performance of vacuum edge surface of polymer insulator |
| CN104371133A (en) * | 2014-11-04 | 2015-02-25 | 天津学子电力设备科技有限公司 | Method for eliminating electrostatic charges on surface of basin-type insulator in GIS |
| CN105761857A (en) * | 2016-02-24 | 2016-07-13 | 西安交通大学 | Method for fluorinating insulator through use of CF4 plasma |
| CN106565982A (en) * | 2016-11-18 | 2017-04-19 | 重庆大学 | Method for improving corona resistance of polyethylene |
| CN106782941A (en) * | 2016-12-22 | 2017-05-31 | 同济大学 | A kind of method for improving the resistance to discharge performance of epoxy insulation in Electrode in Gas Insulated System |
| CN107216483A (en) * | 2017-06-15 | 2017-09-29 | 重庆大学 | A kind of method for lifting epoxy resin edge flashing intensity |
| CN107326331A (en) * | 2017-05-27 | 2017-11-07 | 国网湖北省电力公司检修公司 | A kind of process for improving epoxy resins insulation Work tool surface dielectric performance |
| CN109942793A (en) * | 2019-03-22 | 2019-06-28 | 合肥工业大学 | A kind of Organic fluoride modified epoxy and its preparation method and application improving edge flashing voltage |
| CN111037819A (en) * | 2019-11-01 | 2020-04-21 | 华北电力大学（保定） | Preparation method of epoxy insulation composite material with improved static dissipation characteristic |
| CN111363121A (en) * | 2020-03-26 | 2020-07-03 | 上海稳优实业有限公司 | Method for improving tracking resistance of epoxy resin material |
| CN113628817A (en) * | 2021-08-18 | 2021-11-09 | 天津大学 | Method for modifying surface structure of insulator and application |
| CN113960392A (en) * | 2021-09-14 | 2022-01-21 | 河北工业大学 | Aviation insulating material modification method capable of improving flashover voltage and test system thereof |
| CN114015019A (en) * | 2021-11-05 | 2022-02-08 | 合肥工业大学 | Method for improving surface flashover voltage of epoxy resin insulating material |
| CN116622110A (en) * | 2023-05-22 | 2023-08-22 | 国网河南省电力公司电力科学研究院 | Treatment method for optimizing direct current flashover and charge aggregation phenomena on surface of epoxy insulator |
-
2011
- 2011-12-23 CN CN2011104404886A patent/CN102585165A/en active Pending
Non-Patent Citations (1)
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| 刘亚强等: "氟气处理对环氧树脂表面电荷积聚的影响", 《第十三届全国工程电介质学术会议论文集》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205009A (en) * | 2012-11-21 | 2013-07-17 | 天津学子电力设备科技有限公司 | Preparation method of corona resistant polyimide film having three-layer structure |
| CN103159975A (en) * | 2012-11-22 | 2013-06-19 | 天津学子电力设备科技有限公司 | Device enabling surface charge of polyimide film to dissipate rapidly |
| CN103280280A (en) * | 2013-04-25 | 2013-09-04 | 西北核技术研究所 | Method for improving flashover performance of vacuum edge surface of polymer insulator |
| CN103280280B (en) * | 2013-04-25 | 2016-09-21 | 西北核技术研究所 | A kind of method improving polymer insulator vacuum edge flashing performance |
| CN104371133A (en) * | 2014-11-04 | 2015-02-25 | 天津学子电力设备科技有限公司 | Method for eliminating electrostatic charges on surface of basin-type insulator in GIS |
| CN105761857A (en) * | 2016-02-24 | 2016-07-13 | 西安交通大学 | Method for fluorinating insulator through use of CF4 plasma |
| CN106565982A (en) * | 2016-11-18 | 2017-04-19 | 重庆大学 | Method for improving corona resistance of polyethylene |
| CN106782941B (en) * | 2016-12-22 | 2018-05-08 | 同济大学 | A kind of method for improving the resistance to discharge performance of epoxy insulation in Electrode in Gas Insulated System |
| CN106782941A (en) * | 2016-12-22 | 2017-05-31 | 同济大学 | A kind of method for improving the resistance to discharge performance of epoxy insulation in Electrode in Gas Insulated System |
| CN107326331A (en) * | 2017-05-27 | 2017-11-07 | 国网湖北省电力公司检修公司 | A kind of process for improving epoxy resins insulation Work tool surface dielectric performance |
| CN107216483A (en) * | 2017-06-15 | 2017-09-29 | 重庆大学 | A kind of method for lifting epoxy resin edge flashing intensity |
| CN109942793A (en) * | 2019-03-22 | 2019-06-28 | 合肥工业大学 | A kind of Organic fluoride modified epoxy and its preparation method and application improving edge flashing voltage |
| CN111037819A (en) * | 2019-11-01 | 2020-04-21 | 华北电力大学（保定） | Preparation method of epoxy insulation composite material with improved static dissipation characteristic |
| CN111037819B (en) * | 2019-11-01 | 2021-09-14 | 华北电力大学（保定） | Preparation method of epoxy insulation composite material with improved static dissipation characteristic |
| CN111363121A (en) * | 2020-03-26 | 2020-07-03 | 上海稳优实业有限公司 | Method for improving tracking resistance of epoxy resin material |
| CN113628817A (en) * | 2021-08-18 | 2021-11-09 | 天津大学 | Method for modifying surface structure of insulator and application |
| CN113960392A (en) * | 2021-09-14 | 2022-01-21 | 河北工业大学 | Aviation insulating material modification method capable of improving flashover voltage and test system thereof |
| CN114015019A (en) * | 2021-11-05 | 2022-02-08 | 合肥工业大学 | Method for improving surface flashover voltage of epoxy resin insulating material |
| CN114015019B (en) * | 2021-11-05 | 2024-03-01 | 合肥工业大学 | Method for improving surface flashover voltage of epoxy resin insulating material |
| CN116622110A (en) * | 2023-05-22 | 2023-08-22 | 国网河南省电力公司电力科学研究院 | Treatment method for optimizing direct current flashover and charge aggregation phenomena on surface of epoxy insulator |
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Application publication date: 20120718 |