CN104937682A - Electrically insulating composite material and electrical device comprising the same - Google Patents
Electrically insulating composite material and electrical device comprising the same Download PDFInfo
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- CN104937682A CN104937682A CN201380070844.7A CN201380070844A CN104937682A CN 104937682 A CN104937682 A CN 104937682A CN 201380070844 A CN201380070844 A CN 201380070844A CN 104937682 A CN104937682 A CN 104937682A
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Abstract
The present invention relates to an electrical device in the form of a paper or a pressboard, wherein the electrically insulating composite material is obtained through post-treating by electron beam irradiation treatment, gamma irradiation treatment or X-ray irradiation treatment.
Description
Technical field
The present invention relates to a kind of electrical insulating composition material for paper or laminated form, wherein said electrical insulating composition material is obtained by the post-processing approach via treatment with irradiation.
Background technology
The insulation of oil immersion-type distribution and power transformer can pass through paper and the pressing plate realization of cellulose or polymer.Cellulose paper or pressing plate are mainly used in having in the transformer required compared with low thermal stability, and polymer paper or pressing plate are mainly used in having in the transformer that high thermal stability requires.The Thermal Shield of Nomex and 3M of Du Pont is common commercial polymer paper or pressing plate.Typically, cellulose paper or pressing plate are more widely used than polymer paper or pressing plate.Main cause be cellulose paper or pressing plate cost than polymer make much lower.But the use at high temperature of cellulose paper or pressing plate is limited to the low thermal stability of cellulosic material.On the other hand, because polymer paper or pressing plate have higher cost, therefore its application is also not satisfied.In addition, for some application, need paper or pressing plate not only to have suitable high thermal stability, also there is the mechanical performance of increase, better electrical insulation capability can be provided to make paper or pressing plate.
In the past, existing trial is improved the performance of paper or pressing plate, and major part is attempted mainly concentrating on and selected different polymer and different processing methods.Treatment with irradiation, such as electron beam irradiation process, gamma-radiation process and X-ray treatment with irradiation are the effective ways of the crosslink density increasing some polymeric materials, thereby increase the mechanical performance of polymer.But, until at present, in the application relating to electrically-insulating paper or pressing plate, also rarely have the report about treatment with irradiation.
US 6 824 728 B2 relates to a kind of method of crosslinked polyacrylate composition, and wherein, by optionally irradiating contact adhesive composition with electron beam, polymer only solidifies in specific structure, therefore, can prepare structurized pressure sensitive adhesive composition.
US 3 707 692 discloses a kind of by carrying out impregnation of fibers element with comprising the composition of cellulose swelling agents with the compound that can be cross-linked with cellulosic molecule, increases the method for the dimensional stability of cellulosic material thus.Describedly crosslinked to occur when there is not acidic catalyst at elevated temperatures, and crosslinked cellulosic material can be used as the insulator in electrical devices.
Still need to provide the composite materials, the thermal stability that described performance is such as improved and the better mechanical performance that have and improve the paper of performance or the electric insulation of laminated form.
Summary of the invention
The invention provides the composite materials of the electric insulation of a kind of paper or laminated form, wherein said electrical insulating composition material can be obtained by the post processing mode via treatment with irradiation.
One aspect of the invention relates to the treatment with irradiation for reprocessing, and the wherein said treatment with irradiation for reprocessing is that electron beam irradiation, gamma-radiation and X-ray irradiate or it combines.According to one embodiment of the invention, carry out under described electron beam irradiation, gamma-radiation and X-ray are radiated at ambient air atmosphere or when inert gas injecting.According to another embodiment of the invention, the dosage that electron beam irradiation, gamma-radiation and X-ray irradiate is 30kGy to 300kGy, preferred 50kGy to 200kGy.
Another aspect of the present invention relates to electrical insulating composition material, and wherein said composite materials is made up of fiber and fine strip body.According to one embodiment of the invention, described fiber comprises at least one in following fiber: pet fiber, polyethylene naphthalate fiber, PTT fiber, polybutylene terephthalate (PBT), polyacrylonitrile fibre, Fanglun 1313, Fanglun 1414, polysulfonamide fibre, polyphenylene sulfide fibre, polyphenylether fibre, polyether sulfone fiber, polyetheretherketonefiber fiber, polyether-imide fiber and cellulose fibre.According to another embodiment of the invention, described fine strip body comprises at least one in following fine strip body: polypropylene nitrile fine strip body, PETG fine strip body, PEN fine strip body, PTT fine strip body, polybutylene terephthalate (PBT) fine strip body, poly fine strip body and polysulfonamide fine strip body.
According to one embodiment of the invention, based on the total weight of electrical insulating composition material, the amount of the fiber in electrical insulating composition material is 5 % by weight to 95 % by weight, and the amount of fine strip body is 5 % by weight to 95 % by weight.
According to one embodiment of the invention, described electrical insulating composition material is the form of paper or pressing plate.
Another aspect of the present invention relates to the electrical devices comprising above-mentioned electrical insulating composition material, such as power transformer or motor.
The present inventor finds unexpectedly, irradiates to carry out reprocessing and can provide a kind of and have the mechanical performance of improvement and the electrical devices of thermal stability, especially high-voltage insulating system by using electron beam irradiation, gamma-radiation and X-ray.Specifically, electrical insulating composition material demonstrates significantly different performances after this treatment with irradiation.Such as, the electrical insulating composition material (embodiment 1) prepared by polyacrylonitrile fine strip body and pet fiber, after electron beam irradiation process, the temperature of degraded 5% is elevated to 339 DEG C from 323 DEG C, tensile strength is elevated to about 115MPa from about 100MPa, and compressibility is reduced to 3.1% from 3.5%.
Accompanying drawing explanation
Hereafter exemplarily embodiments of the present invention are described, in accompanying drawing with reference to the accompanying drawing appended by this paper:
Fig. 1 is the indicative flowchart of the method according to one embodiment of the invention.
Embodiment
Hereafter describe embodiments of the present invention in further detail with reference to appended accompanying drawing, in accompanying drawing, show specific embodiment.But other multi-form embodiments also belong to scope disclosed by the invention.In addition, following embodiment provides by way of example, to make content disclosed by the invention more complete, and intactly can pass on the scope of the disclosure of invention to those skilled in the art.
The invention provides the electrical insulating composition material of a kind of paper or laminated form, wherein said electrical insulating composition material can be obtained by the reprocessing via treatment with irradiation.
Preferably, the thickness of pressing plate of the present invention is greater than 0.9mm.More preferably, the thickness of pressing plate is 1 – 12mm, most preferably is 1 – 8mm.The thickness of paper of the present invention is less than 0.9mm, is preferably less than 0.8mm, is more preferably 0.05 – 0.5mm.
Affect the mechanical performance of polymeric material and a key factor of thermal stability is the degree of cross linking.Term is cross-linked for representing that the large molecule of a large amount of originally solvable straight or branched is joined together to form Space network of polymer (cross-linked polymer, network polymers), and it is insoluble, but can only be swelling.Crosslinked may be owing to defining covalent bond or non-covalent bond (coordinate bond, ion physical key, salt-form).Crosslinked and/or can pass through at preformed (in advance) polymer in macromolecular actual manufacture process---it is usually containing functional group---carries out during above reacting.
Usually, the crosslinked of polymer can by heating or irradiating initiation.Due to the poor thermal stability of some electrical insulating composition materials, treatment with irradiation should be the better method carrying out being cross-linked.Treatment with irradiation generally includes ultraviolet light (UV) and irradiates, and electron beam (EB) irradiates, gamma-radiation and X-ray treatment with irradiation.Especially, UV is crosslinked is very simple method, only needs simple coating and several low pressure mercury lamp to carry out.The effect that UV is cross-linked for the polymer composition with low film thickness is good especially.On the other hand, EB, gamma-radiation and X-ray irradiation technique costly, but can be applicable to the crosslinked of larger film thickness and faster web speed on device.
One aspect of the invention relates to the treatment with irradiation for reprocessing, and the wherein said treatment with irradiation for reprocessing is electron beam irradiation process, gamma-radiation process and X-ray treatment with irradiation or its combination.According to one embodiment of the invention, carry out under described electron beam irradiation, gamma-radiation and X-ray are radiated at ambient air atmosphere or when inert gas injecting.
Now think and irradiate by electron beam irradiation, gamma-radiation and X-ray the crosslink density that the reprocessing carried out can increase electrical insulating composition material, can also the degraded of induced material.By using suitable irradiation reprocessing to balance cross-linking reaction and degradation reaction, we can increase thermal stability and the mechanical property of electrical insulating composition material.According to the present invention, the thermal stability of electrical insulating composition material by degrade 5% temperature evaluate, this is well known by persons skilled in the art, and is usually used in this area.Such as, for the electrical insulating composition material prepared by polyacrylonitrile fine strip body and pet fiber (embodiment 1), after EB irradiates, the volume increase of pressing plate only has 35%, well below the pressing plate (50%) not carrying out EB irradiation accordingly, this means that crosslink density increases.In addition, after this EB treatment with irradiation, the temperature of pressing plate degraded 5% is increased to 339 DEG C from 323 DEG C, and the tensile strength of pressing plate is increased to about 115MPa from about 100MPa, the compressibility of pressing plate is reduced to 3.1% from 3.5%, this means that mechanical performance is improved.
Another aspect of the present invention relates to the composite materials of electric insulation, and wherein said composite materials is made up of fiber and fine strip body.Fiber can be polymer fiber.The polymer fiber prepared for paper and pressing plate is short fiber, and it is made up of the common continuous fiber with normal dia usually.Short polymer fiber can process by beating further, to improve its Papermaking Performance.Described fine strip body can be polymer fibrid.Polymer fibrid is a kind of fibrous shot-like particle for bonding, and has irregular shape, and is prepared by polymer solution.
According to one embodiment of the invention, described fiber comprises at least one in following fiber: pet fiber, polyethylene naphthalate fiber, PTT fiber, polybutylene terephthalate (PBT), polyacrylonitrile fibre, Fanglun 1313, Fanglun 1414, polysulfonamide fibre, polyphenylene sulfide fibre, polyphenylether fibre, polyether sulfone fiber, polyetheretherketonefiber fiber, polyether-imide fiber, cellulose fibre and combination thereof.
According to one embodiment of the invention, described fine strip body comprises at least one in following fine strip body: polyacrylonitrile fine strip body, PETG fine strip body, PEN fine strip body, PTT fine strip body, polybutylene terephthalate (PBT) fine strip body, poly fine strip body, polysulfonamide fine strip body and combination thereof.
According to one embodiment of the invention, based on the total weight of electrical insulating composition material, the amount of the fiber in electrical insulating composition material is 5 % by weight to 95 % by weight, preferably 20 % by weight to 60 % by weight.According to another embodiment of the invention, based on the total weight of electrical insulating composition material, the amount of fine strip body is 5 % by weight to 95 % by weight, preferably 40 % by weight to 80 % by weight.
After conducting extensive research, the present inventor finds, being in certain limit temperature, specific dosage does not make preparing the composite materials of electric insulation the degraded of final material damage obtains good balance, this has overall permanence beyond expectation, such as mechanical strength and thermal stability.According to one embodiment of the invention, the suitable dose that electron beam irradiation, gamma-radiation and X-ray irradiate is 30kGy to 300kGy.Better crosslinked in order to obtain, this dosage can be optimized further.According to embodiments more of the present invention, the suitable dose that EB, gamma-radiation and X-ray irradiate is preferably 50kGy to 200kGy.Especially, for the pressing plate prepared by PETG fine strip body and pet fiber, the dosage that preferred EB irradiates is about 200kGy (embodiment 2).More particularly, for the pressing plate prepared by polyacrylonitrile fine strip body and cellulose fibre, the dosage that preferred EB irradiates is about 100kGy (embodiment 4).
Composite materials is electric insulation, and is suitable as the insulating material in electrical devices.Composite materials can be used to the electric insulation in such as electrical devices, and such as, in power transformer, composite materials can be high voltage insulating materials thus.
As mentioned above, electrical insulating composition material can have especially favourable electrical insulation capability in oiliness environment.Therefore, electrical insulating composition material can be at least part immersion oil.
The present invention also provides a kind of electrical devices comprising electrical insulating composition material of the present invention.Electrical devices can be any electrical devices comprising electric insulation, such as power transformer or electric conductor or motor, they especially can benefit from composite materials, such as there is the mechanical performance of improvement, during the manufacture of transformer, insulation height regulates needs less time, and can reduce total insulation thickness.
Especially, electrical devices according to the present invention is power transformer.
Electrical insulating composition material can be the form of paper for insulating in electrical devices, barrier film, barrier, pressure ring, and described electrical devices is as electric conductor, power transformer.The composite materials of electric insulation has electrical insulation characteristics, and it may be used in any electrical devices, and such as, for the insulation of electricity conduit, but electrical insulating composition material is especially favourable in the environment of oiliness, such as, in power transformer.Especially, electrical insulating composition material may be used for the electric insulation diaphragm prepared in transformer coiling.
The electrical insulating composition material of the electrical devices the application of the invention improved obtains.Especially, electrical insulating composition material demonstrates the mechanical property of improvement, as the compressibility improved.
Fig. 1 is the indicative flowchart of the art methods for the preparation of insulating paper and pressing plate, method 1.Fine strip body (2) is provided, fiber (3) is provided.Afterwards fine strip body and fiber are mixed with each other (4).Use nipper afterwards, as the pressing mixts such as laminating machine (5), the pressing plate made to provide the composite materials discussed herein or ground paper etc.Described pressing process also comprises the heating (6) of mixture, dry (7), and mixture is pressed into pressing plate (8).Then, by pressing plate cooling (9).Cooled pressing plate can be cut into the insulating element of expectation, such as, in transformer or any other electrical devices.Such as, can be produced for electric power transformer insulated barrier film, barrier, band or pressure ring by composite materials of the present invention.
Embodiment
The prior art preparation of electrical insulating composition material first according to Fig. 1 of paper or laminated form, then carry out reprocessing by irradiation and obtain.Electrical insulating composition properties of materials measures according to the standard 60641-2 of IEC (International Electrotechnical Commission (IEC)).
Embodiment 1:
Method according to Fig. 1 prepares pressing plate.Solid material for the preparation of pressing plate is the polyacrylonitrile fine strip body (Shanghai technology fiber Co., Ltd of blue nation) of 60 % by weight and the pet fiber (Woongjin Chemical Co., Ltd.) of 40 % by weight.The basic weight of pressing plate is 2420g/m
2, thickness is 2mm, and density is 1.21g/cm
3.
Use the electron beam source of 1.5MeV to carry out reprocessing to pressing plate, irradiate and at room temperature carry out in surrounding air.Pressing plate sample is held in place in the steel disk of the opening on conveyer belt, and it through electron beam scanning angle, carries out 6 times with the speed of 3m/min.Pressing plate sample irradiates through 25kGy each time, and the accumulated dose put on sample is 150kGy.
For comparing the network density in pressing plate, based on " Cross-Linking-Effect onPhysical Properties of Polymers " (Nielsen, L.E., Journal ofMacromolecular Science, Part C, 1969,3,69-103) described by method carry out swelling mensuration.In this experiment, the change in volume of the rear fender immersing certain hour in solvent is at a certain temperature determined.
For carrying out each swelling test, each pressing plate adopts 3 samples carry out or do not carry out treatment with irradiation, and sample is cut into the size of about 25*15*2mm, and accuracy is 0.05mm.Sample is dipped in the metacresol of 100mL, at 70 DEG C 24 hours.Afterwards, shifted out by sample from solvent, the short time is cooled to room temperature, remeasures size.After swelling, the volume of non-irradiated pressing plate increases to about 50%, and irradiate the volume of rear fender increase to about 35%.
The temperature of the degraded 5% of untreated pressing plate is measured in air atmosphere by thermogravimetric analyzer (TGA), is about 323 DEG C, and the pressing plate after process is 339 DEG C.The tensile strength of untreated pressing plate is about 100MPa, and the tensile strength of the pressing plate of process is about 115MPa; The compressibility of untreated pressing plate is about 3.5%, and the compressibility of pressing plate after process is about 3.1%.
Use this embodiment method to carry out another test, different be only that pressing plate uses the dosage of 300kGy to irradiate in atmosphere, result illustrates, the character of the pressing plate of process and the character of untreated pressing plate closely similar.Think that exposure dose higher in atmosphere can lure higher pressing plate palliating degradation degree into.
This embodiment method is used to carry out another test, difference is only that pressing plate uses the dosage of 150kGy to irradiate in nitrogen atmosphere, result illustrates, after the exposure dose of 150kGy is irradiated in nitrogen, the character of the pressing plate of process is slightly better than the character of untreated pressing plate.We think that nitrogen atmosphere can avoid some the competitive oxidation processes during treatment with irradiation, and this is favourable for final material property.
Embodiment 2
Method according to Fig. 1 prepares pressing plate.Solid material for the preparation of pressing plate is the PETG fine strip body (Shanghai technology fiber Co., Ltd of blue nation) of 60 % by weight and the pet fiber of 40 % by weight.The basic weight of pressing plate is 1160g/m
2, thickness is 1mm, and density is 1.16g/cm
3.
Use the electron beam source of 1.5MeV to carry out reprocessing to pressing plate, irradiate and at room temperature carry out in surrounding air.Pressing plate sample is held in place in the steel disk of the opening on conveyer belt, and it through electron beam scanning angle, carries out 8 times with the speed of 3m/min.Pressing plate sample irradiates through 25kGy each time, and the accumulated dose put on sample is 200kGy.
For carrying out each swelling test, each pressing plate adopts 3 samples carry out or do not carry out treatment with irradiation, and sample is cut into the size of about 25*15*1mm, and accuracy is 0.05mm.Sample is dipped in the metacresol of 100mL, at 70 DEG C 24 hours.Afterwards, shifted out by sample from solvent, the short time is cooled to room temperature, remeasures size.After swelling, the volume of non-irradiated pressing plate increases to about 48%, and irradiate the volume of rear fender increase to about 32%.When sample to immerse in the metacresol of 100mL at 90 DEG C after 14 hours, the volume after non-irradiated pressing plate is swelling increases to about 86%, and irradiate the volume of rear fender increase to about 54%.
The temperature of the degraded 5% of untreated pressing plate is measured in air atmosphere by thermogravimetric analyzer (TGA), is about 360 DEG C, and the pressing plate after process is 377 DEG C.The tensile strength of untreated pressing plate is about 80MPa, and the tensile strength of the pressing plate of process is about 90MPa; The compressibility of untreated pressing plate is about 3.4%, and the compressibility of pressing plate after process is about 3.0%.
Embodiment 3
Method according to Fig. 1 prepares pressing plate.Solid material for the preparation of pressing plate be the polyacrylonitrile fine strip body of 60 % by weight, the Fanglun 1313 (Yantai Tayho Advanced Materials Co., Ltd.) of 10 % by weight and 30 % by weight polyethylene naphthalate fiber.The basic weight of pressing plate is 1120g/m
2, thickness is 1mm, and density is 1.12g/cm
3.
Use the gamma-irradiation source of 1.5MeV to carry out reprocessing to pressing plate, irradiate and at room temperature carry out in surrounding air.Pressing plate sample is held in place in the steel disk of the opening on conveyer belt, and it through gamma-irradiation scan angle, carries out 8 times with the speed of 2m/min.Pressing plate sample irradiates through 25kGy each time, and the accumulated dose put on sample is 200kGy.
For carrying out each swelling test, each pressing plate adopts 3 samples carry out or do not carry out treatment with irradiation, and sample is cut into the size of about 25*15*1mm, and accuracy is 0.05mm.Sample is dipped in the metacresol of 100mL, at 70 DEG C 24 hours.Afterwards, shifted out by sample from solvent, the short time is cooled to room temperature, remeasures size.After swelling, the volume of the pressing plate of non-treatment with irradiation increases to about 60%, and irradiate the volume of rear fender increase to about 50%.
The temperature of the degraded 5% of untreated pressing plate is measured in air atmosphere by thermogravimetric analyzer (TGA), is about 370 DEG C, and the pressing plate after process is 380 DEG C.The tensile strength of untreated pressing plate is about 100MPa, and the tensile strength of the pressing plate of process is about 110MPa; The compressibility of untreated pressing plate is about 3.2%, and the compressibility of pressing plate after process is about 2.9%.
Embodiment 4
Method according to Fig. 1 prepares pressing plate.Solid material for the preparation of pressing plate is the polyacrylonitrile fine strip body of 20 % by weight and the cellulose fibre of 80 % by weight.The basic weight of pressing plate is 1140g/m
2, thickness is 1mm, and density is 1.14g/cm
3.
Use the electron beam source of 1.5MeV to carry out reprocessing to pressing plate, irradiate and at room temperature carry out in surrounding air.Pressing plate sample is held in place in the steel disk of the opening on conveyer belt, and it through electron beam scanning angle, carries out 4 times with the speed of 3m/min.Pressing plate sample irradiates through 25kGy each time, and the accumulated dose put on sample is 100kGy.
The temperature of the degraded 5% of untreated pressing plate is measured in air atmosphere by thermogravimetric analyzer (TGA), is about 316 DEG C, and the pressing plate after process is 325 DEG C.The tensile strength of untreated pressing plate is about 105MPa, and the tensile strength of the pressing plate of process is about 115MPa; The compressibility of untreated pressing plate is about 4.2%, and the compressibility of pressing plate after process is about 3.9%.
Claims (11)
1. an electrical insulating composition material, it is paper or laminated form, and wherein said electrical insulating composition material is obtained by the reprocessing via treatment with irradiation.
2. electrical insulating composition material according to claim 1, the described treatment with irradiation wherein for reprocessing is electron beam irradiation process, gamma-radiation process, X-ray treatment with irradiation, or its combination.
3. electrical insulating composition material according to claim 1 and 2, wherein said electron beam irradiation process, gamma-radiation process and X-ray treatment with irradiation are carried out in surrounding air or when inert gas injecting.
4. the electrical insulating composition material according to any one of claim 1-3, the dosage that wherein said electron beam irradiation, gamma-radiation and X-ray irradiate is 30kGy to 300kGy, preferred 50kGy to 200kGy.
5. electrical insulating composition material according to claim 1, wherein said electrical insulating composition material is made up of fiber and fine strip body.
6. electrical insulating composition material according to claim 5, wherein said fiber comprises at least one in following fiber: pet fiber, polyethylene naphthalate fiber, PTT fiber, polybutylene terephthalate (PBT), polyacrylonitrile fibre, Fanglun 1313, Fanglun 1414, polysulfonamide fibre, polyphenylene sulfide fibre, polyphenylether fibre, polyether sulfone fiber, polyetheretherketonefiber fiber, polyether-imide fiber and cellulose fibre.
7. electrical insulating composition material according to claim 5, wherein said fine strip body comprises at least one in following fine strip body: polypropylene nitrile fine strip body, PETG fine strip body, PEN fine strip body, PTT fine strip body, polybutylene terephthalate (PBT) fine strip body, poly fine strip body and polysulfonamide fine strip body.
8. electrical insulating composition material according to claim 5, wherein, based on the total weight of described electrical insulating composition material, the amount of the fiber in electrical insulating composition material is 5 % by weight to 95 % by weight, and the amount of fine strip body is 5 % by weight to 95 % by weight.
9. an electrical devices, it comprises the electrical insulating composition material according to any one of claim 1-8.
10. electrical devices according to claim 9, wherein said electrical devices is power transformer or motor.
11. electrical devices according to claim 9 or 10, wherein said electrical insulating composition material is barrier film for insulating, barrier, band, the conductor of paper bag or pressure ring form.
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| CN201380070844.7A CN104937682A (en) | 2013-03-01 | 2013-05-07 | Electrically insulating composite material and electrical device comprising the same |
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| CNPCT/CN2013/072081 | 2013-03-01 | ||
| CN201380070844.7A CN104937682A (en) | 2013-03-01 | 2013-05-07 | Electrically insulating composite material and electrical device comprising the same |
| PCT/CN2013/075262 WO2014131245A1 (en) | 2013-03-01 | 2013-05-07 | Electrically insulating composite material and electrical device comprising the same |
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| CN106906689A (en) * | 2017-03-06 | 2017-06-30 | 陕西科技大学 | A kind of polyamine epichlorohydrin resin self-crosslinking polyacrylonitrile fibre paper and preparation method thereof |
| WO2018032269A1 (en) * | 2016-08-15 | 2018-02-22 | Abb Schweiz Ag | Electrically insulating composite material and electrical product |
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| WO2018032269A1 (en) * | 2016-08-15 | 2018-02-22 | Abb Schweiz Ag | Electrically insulating composite material and electrical product |
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| CN106906689B (en) * | 2017-03-06 | 2018-06-05 | 陕西科技大学 | A kind of polyamine epichlorohydrin resin self-crosslinking polyacrylonitrile fibre paper and preparation method thereof |
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