CN105062074A - Direct-current ultrahigh-voltage insulation composition, and preparation method and use thereof - Google Patents
Direct-current ultrahigh-voltage insulation composition, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a direct-current ultrahigh-voltage insulation composition, and a preparation and use thereof. The composition comprises the following components: (A) graphene nanosheets; (B) layered double hydroxides; (C) a coupling agent; and (D) deionized water. The volume of the graphene nanosheets is 0.025vol% to 0.1vol% of that of the layered double hydroxides. The preparation method comprises the following steps of wet-milling the graphene nanosheets and the laminated metal complex hydroxides in a ball-milling machine, adding the coupling agent, and then dry-milling the mixture. The composition disclosed by the invention has excellent tracking resistance, electric corrosion resistance, and flame retardant property; the mechanical property of the composition is also effectively improved; and the composition can be used for preparing insulation materials of direct-current ultrahigh-voltage transmission lines.
Description
Technical field
The invention belongs to Material Field, particularly, the present invention relates to a kind of for direct-current ultra high voltage insulation composition, preparation method and its usage.
Background technology
In high-voltage transmission network, high molecular polymer is under the insulating material of matrix is in high voltage electric field discharge environment for a long time, and its surface causes high molecular polymer to decompose ablation due to arc-over and the high temperature that causes, thus causes insulation failure.Improve insulating material anti creepage trace and electrical insulation capability typically by a large amount of interpolation aluminium hydroxide or aluminum oxide, voltage of its application power transmission network is low, cannot be applied to direct-current ultra high voltage power transmission network.
The metal nanoparticle of minute quantity adds in polymeric system by CN104327456A, improves volume specific resistance and the disruptive strength of material owing to producing Coulomb blockade effect.But this prior art only discloses and metal nanoparticle added the volume specific resistance and disruptive strength that can improve material, do not relate to anti creepage trace and performance is damaged in galvanic corrosion.
CN103787322A adopts the chitosan-based material of water-soluble polymer as reductive agent and stablizer, and layered silicate prepares Graphene as stablizer and template, obtains one and supports Graphene laminated nm-silicate composite material.What this invention mainly solved is difficult to the problem of stable dispersion for the strong toxicity in Graphene preparation process and product, and it does not relate to anti creepage trace equally and performance is damaged in galvanic corrosion.
Porous graphene and clay are combined into the matrix material of porous by CN103143319A, for heavy metal and organic absorption.The strong adsorptive power of what this invention mainly utilized is Graphene, it does not relate to anti creepage trace equally and performance is damaged in galvanic corrosion.
CN104371144A prepares hydrotalcite load Graphene fire retardant, for polymer-modified flame retardant properties by coprecipitation method.This prior art mainly utilizes Graphene to improve flame retardant properties, and performance is damaged in not mentioned anti creepage trace and galvanic corrosion.
CN104392843A discloses a kind of three-layer laminated metal hydroxides nanometer sheet/graphene aerogel matrix material and preparation method.Layered metal hydroxides nanometer sheet/graphene aerogel material is made up of three-dimensional grapheme aerogel and two-dimensional layer metal hydroxides nanometer sheet, what layered metal hydroxides nanometer sheet was orderly is distributed in graphene aerogel surface and interlayer, forms a kind of tridimensional network.This prior art is all form three-dimensional conductive path by adding a large amount of three-dimensional graphemes, and it cannot be directly used in insulating material.
CN103275408A discloses the preparation method of a kind of Graphene/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material: comprise and being dissolved in graphene oxide colloid by carbon nanotube, stir and utilize ultrasonic wave disperse make it be uniformly dispersed after add M
2+salt and Al
3+add urea after salt, obtain graphene/carbon nano-tube/layered double-hydroxide after back flow reaction composite assembled, by composite assembled mix with polystyrene resin after melt extrude and obtain pipe/polyhenylethylene nano flame-proof composite material.This prior art is by adding a large amount of Graphenes to realize its fire retardation, and it does not consider the impact added in a large number insulating property of Graphene.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to provide a kind of for direct-current ultra high voltage insulation composition and preparation method thereof.
In the present invention, described " extra-high voltage " to voltage at more than 1000kV.
In order to achieve the above object, present invention employs following technical scheme:
A kind of for direct-current ultra high voltage insulation composition, it comprises following component:
(A) graphene nanometer sheet;
(B) layered composite metal hydroxides;
The volume of described graphene nanometer sheet is 0.025 ~ 0.1vol% of layered composite metal hydroxides volume.
Graphene has unique two-dimensional layered structure, there is excellent obstruct flame retardant properties and heat-resistant stability, sealing coat can be formed on surface, prevent the continuation of polymkeric substance under arcing from decomposing, thus effectively can improve heat-resistant stability that polymkeric substance is the insulating material of matrix, anti creepage trace and galvanic corrosion and damage performance.In addition, the present invention is by selecting the content of the graphene nanometer sheet far below the percolation threshold that can form conductive network, and overcome the problem that Graphene itself has very strong electroconductibility, what make Graphene adds the insulativity not affecting insulating material.
Layered composite metal hydroxides has excellent absorption, obstruct and heat-resistant stability, and the laminate structure of its houghite is conducive to carrying out compound with Graphene.A small amount of Graphene is combined with layered composite metal hydroxides by the present invention, utilizes composite synergistic effect between the two, while raising insulating material anti creepage trace and galvanic corrosion damage performance, do not affect its insulating property.In addition, graphene nanometer sheet add the mechanical property that can also improve insulating material.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described insulation composition different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".Exemplary as, of the present inventionly can also comprise carbon nanotube lower than percolation threshold content for direct-current ultra high voltage insulation composition.
In the present invention, the volume of described graphene nanometer sheet is 0.025 ~ 0.1vol.% of layered composite metal hydroxides volume, such as 0.03vol.%, 0.035vol.%, 0.04vol.%, 0.045vol.%, 0.05vol.%, 0.055vol.%, 0.06vol.%, 0.065vol.%, 0.07vol.%, 0.075vol.%, 0.08vol.%, 0.085vol.%, 0.09vol.% or 0.095vol.%, preferably 0.04 ~ 0.085vol%, further preferred 0.045 ~ 0.07vol%.
In the present invention, graphene nano chip size is too large, easily forms conductive path, affects insulating property.Preferably, the thickness of described graphene nanometer sheet is 1 ~ 20nm, preferably 5 ~ 10nm; Length is 100nm ~ 20 μm, preferred 300nm ~ 5 μm; Specific surface area is 30 ~ 1500m
2/ g.
Preferably, layered double-metal hydroxide has following general formula:
[M1
a 2+M2
b 2+M3
c 3+M4
d 3+(OH)
y]
x+(zA
n-)·vH
2O
Wherein M1 and M2 is divalent metal, and M1 includes but not limited to Ca
2+, Mg
2+, Zn
2+, Cu
2+, Co
2+or Ni
2+in any one, preferred Ca
2+, Mg
2+or Zn
2+in any one; M2 includes but not limited to Ca
2+, Mg
2+, Zn
2+, Cu
2+, Co
2+or Ni
2+in any one, preferred Co
2+, Ni
2+or Cu
2+in any one; M3 and M4 is trivalent metal cation, and M3 includes but not limited to Al
3+, Cr
3+, Fe
3+or Ce
3+in any one, preferred Al
3+or Fe
3+; M4 includes but not limited to Al
3+, Cr
3+, Fe
3+or Ce
3+in any one, preferred Cr
3+or Ce
3+;
A+b equals 1-x; C+d equals x, and wherein, x is (M3
3++ M4
3+)/(M1
2++ M2
2++ M3
3++ M4
3+) molar ratio, be 0.1 ~ 0.9 (such as 0.2,0.3,0.4,0.5,0.6,0.7 or 0.8), preferably 0.2 ~ 0.8, more preferably 0.5 ~ 0.7; Y is 1 ~ 6 (such as 1.5,2,2.5,3,3.5,4,4.5,5 or 5.5), preferably 2 ~ 4;
A
n-represent the tradable negatively charged ion of interlayer, include but not limited to nitrate radical, sulfate radical, lactate, amino acid, chlorion, carbonate, z is anion mol quantity, and n is negatively charged ion valence mumber, and wherein zn equals [2 (a+b)+3 (c+d)-y]; V is interlayer crystal water quantity, is 0.1 ~ 5 (such as 0.2,0.5,1,1.5,2,2.5,3,3.5,4 or 4.5), preferably 0.5 ~ 3.
In above-mentioned general formula, be not construed as limiting separately a and b, its demand fulfillment be a+b's and be 1-x.
Layered composite metal hydroxides of the present invention, it is containing at least one divalent metal, and containing at least one trivalent metal cation.
Preferably, described insulation composition also comprises (C) coupling agent, and component of the present invention (C) coupling agent is common silane coupling agent, can select containing not isoplastic silane coupling agent according to different polymeric matrixs.
Preferably, (C) coupling agent is 1:5 ~ 1:70, such as 1:10,1:20,1:30,1:40,1:50 or 1:60 with the weight ratio of (B) layered composite metal hydroxides, preferred 1:9 ~ 1:50, more preferably 1:12 ~ 1:45.
Preferably, described insulation composition also comprises (D) solvent.
Preferably, component of the present invention (D) solvent is 1:1.25 ~ 1:3 with the weight ratio of (B) layered composite metal hydroxides, such as 1:1.5,1:1.7,1:1.9,1:2.1,1:2.3,1:2.5,1:2.7 or 1:2.9, preferred 1:1.5 ~ 1:2.5.
Preferably, described solvent is deionized water.
Two of object of the present invention is to provide a kind of preparation method for direct-current ultra high voltage insulation composition, comprises the steps:
(I) graphene nanometer sheet is added ultrasonic disperse in solvent, then add the divalence and trivalent metal salt or oxide compound of preparing layered composite metal hydroxides, stir, then put into ball mill wet-milling, and post-drying;
(II) material obtained after oven dry is put into ball mill for dry grinding again;
Optionally, step (III) is carried out:
(III) coupling agent dry grinding is added.
In the present invention, described " divalence and trivalent metal salt or oxide compound " namely, " divalent metal salt or oxide compound " and " trivalent metal salt or oxide compound ".
In the present invention, first added in solvent by graphene nanometer sheet and carry out ultrasonic disperse, be conducive to the compound of graphene nanometer sheet and laminated metal complex hydroxide, dispersity is high, can significantly improve the various aspects of performance of product.
Preferably, the temperature of step (I) ultrasonic disperse is 25 ~ 45 DEG C, and the time of ultrasonic disperse is 20 ~ 90min.
Preferably, the rotating speed of step (I) ball mill is 200 ~ 1000r/min, preferred 350r/min ~ 800r/min, and the wet-milling time is 200min ~ 660min, preferred 300min ~ 450min.
Preferably, step (II) drum's speed of rotation is 200 ~ 700r/min, preferred 350r/min ~ 600r/min, and the dry grinding time is 20min ~ 360min, preferred 30min ~ 240min.
Preferably, step (III) drum's speed of rotation is 200r/min ~ 500r/min, preferred 350r/min ~ 450r/min, and Ball-milling Time is 20min ~ 360min, preferred 30min ~ 240min.
The present invention prepares Graphene/layered hydroxide composition by adopting ball mill alternation of wetting and drying to carry out ball milling, does not affect its insulating property, have method simple simultaneously, be convenient to industrialized advantage while raising material anti creepage trace and galvanic corrosion damage performance.
Three of object of the present invention is to provide a kind of as above for the purposes of direct-current ultra high voltage insulation composition, and it is for the preparation of direct-current ultra high voltage transmission line insulator device.
Four of object of the present invention is to provide a kind of for direct-current ultra high voltage insulating composite material, and it contains direct-current ultra high voltage insulation composition as above and polymeric matrix.
Preferably, the quality of described direct-current ultra high voltage insulation composition accounts for 5 ~ 30%, such as 6%, 10%, 15%, 20% or 25% of direct-current ultra high voltage insulation composition and polymer-based carbon weight summation.The content of direct-current ultra high voltage insulation composition very little, cannot realize the raising of electrical property, and content is too many, then significantly can reduce mechanical property.
Preferably, described polymeric matrix is the mixture of any one or at least two kinds in silicon rubber, epoxy resin, polyethylene or tetrafluoroethylene.
The above-mentioned direct-current ultra high voltage insulation composition that is used for containing graphene nanometer sheet/laminated metal complex hydroxide is evenly spread in polymeric matrix by a certain percentage, the insulating composite material anti creepage trace of gained and galvanic corrosion are damaged performance and are improved largely, in addition, the mechanical property of insulating composite material have also been obtained and significantly improves, and can be used for the preparation of direct-current ultra high voltage transmission line insulator device.
Compared with the prior art, the present invention has following beneficial effect:
(1) the present invention is by selecting the content of the graphene nanometer sheet lower than the percolation threshold that can form conductive network, overcomes the problem that Graphene itself has very strong electroconductibility, makes not affect its insulativity adding of Graphene.
(2) laminated metal complex hydroxide has excellent absorption, obstruct and heat-resistant stability, the laminate structure of its houghite is conducive to carrying out compound with Graphene, a small amount of Graphene is combined with laminated metal complex hydroxide by the present invention, utilize composite synergistic effect between the two, while raising insulating material anti creepage trace and galvanic corrosion damage performance, do not affect its insulating property;
(3) the present invention carries out ball milling for the preparation of direct-current ultra high voltage insulation composition by adopting ball mill alternation of wetting and drying, its insulating property are not affected while raising material anti creepage trace and galvanic corrosion damage performance, there is method simple simultaneously, be convenient to industrialized advantage.
(4) evenly spread to above-mentioned by a certain percentage in polymeric matrix for direct-current ultra high voltage insulation composition, the insulating composite material anti creepage trace of gained and galvanic corrosion are damaged performance and are improved largely, and mechanical property also significantly improves.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Its anti creepage trace and galvanic corrosion are damaged test and are pressed GB6553-2003 mensuration, and alternating current breakdown strength test measures according to GBT1695-2005, and measuring mechanical property measures according to GB/T528-2009 and GB/T529-2008.
Embodiment 1
By 0.0063g graphene nanometer sheet, (thickness is 1nm, and length is 100nm, and specific surface area is 1500m
2/ g) add in 20ml deionized water, the ultrasonic 60min of normal temperature, adds 8.97g calcium oxide, 13.74g iron nitrate and 2.6g cerous nitrate, stir, put into ball mill wet-milling, drum's speed of rotation is 200r/min, Ball-milling Time is 660min, then put into baking oven to dry, then put into ball mill dry grinding, drum's speed of rotation is 700r/min, Ball-milling Time is 20min, obtains Graphene/[Ca
0.8fe
0.17ce
0.03(OH)
2] (NO
3)
0.20.1H
2o composition.Then add 5.1g vinyltriethoxysilane ball milling, drum's speed of rotation is 200r/min, and Ball-milling Time is 360min, obtains the Graphene/[Ca of modification
0.8fe
0.17ce
0.03(OH)
2] (NO
3)
0.20.1H
2o composition.Get its 5g to join in 95g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 1.5g and hydroxy silicon oil 3.5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv6h, corrosion depth 1.9mm, tensile strength 3.7MPa, elongation at break 679%, tear strength 6.8kN/m, alternating current breakdown intensity 20kV/mm.
Embodiment 2
By 0.02g graphene nanometer sheet, (thickness is 20nm, and length is 20 μm, and specific surface area is 30m
2/ g) add in 6.8ml deionized water, the ultrasonic 60min of normal temperature, adds 7.5g calcium oxide, 6.5g cupric chloride and 6.4g aluminum chloride, stir, put into ball mill wet-milling, drum's speed of rotation is 1000r/min, Ball-milling Time is 300min, then put into baking oven to dry, then put into ball mill dry grinding, drum's speed of rotation is 200r/min, Ball-milling Time is 360min, obtains Graphene/[Ca
0.67cu
0.19al
0.24(OH)
2] (Cl)
0.443H
2o composition.Then add 0.3g vinyltriethoxysilane ball milling, drum's speed of rotation is 700r/min, and Ball-milling Time is 20min, obtains the Graphene/[Ca of modification
0.67cu
0.19al
0.24(OH)
2] (Cl)
0.443H
2o composition.Get its 30g to join in 70g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 2.5g and hydroxy silicon oil 4.5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv9.5h, corrosion depth 2.2mm, tensile strength 6.3MPa, elongation at break 349%, tear strength 12.8kN/m, alternating current breakdown intensity 31kV/mm.
Embodiment 3
By 0.023g graphene nanometer sheet, (thickness is 5nm, and length is 300nm, and specific surface area is 750m
2/ g) add in 23ml deionized water, the ultrasonic 60min of normal temperature, adds 16.84g magnesium sulfate, 7.45g single nickel salt, 13.32g Tai-Ace S 150 and 20.2g ferric sulfate, stir, put into ball mill wet-milling, drum's speed of rotation is 800r/min, and Ball-milling Time is 300min, then puts into baking oven and dries, put into ball mill dry grinding again, drum's speed of rotation is 600r/min, and Ball-milling Time is 30min, obtains Graphene/[Mg
0.41ni
0.17al
0.12fe
0.3(OH)
2] (SO
4)
0.210.8H
2o composition.Then add 1.16g vinyl three ('beta '-methoxy oxyethyl group) silane ball milling, drum's speed of rotation is 450r/min, and Ball-milling Time is 30min, obtains the Graphene/[Mg of modification
0.41ni
0.17al
0.12fe
0.3(OH)
2] (SO
4)
0.210.8H
2o composition.Get its 26g to join in 74g room temperature vulcanized silicone rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 2.5g and hydroxy silicon oil 3.5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv10h, corrosion depth 2.4mm, tensile strength 7.1MPa, elongation at break 460%, tear strength 11.3kN/m, alternating current breakdown intensity 28kV/mm.
Embodiment 4
By 0.026g graphene nanometer sheet, (thickness is 10nm, and length is 5 μm, and specific surface area is 47m
2/ g) add in 20ml deionized water, the ultrasonic 60min of normal temperature, adds 2.5g calcium oxide, 5.13g magnesium nitrate and 23g aluminum nitrate, stir, put into ball mill wet-milling, drum's speed of rotation is 350r/min, Ball-milling Time is 450min, then put into baking oven to dry, then put into ball mill dry grinding, drum's speed of rotation is 350r/min, Ball-milling Time is 240min, obtains Graphene/[Ca
0.35mg
0.16al
0.49(OH)
2] (NO
3)
0.490.5H
2o composition.Then add 3.4g vinyltriethoxysilane ball milling, drum's speed of rotation is 500r/min, and Ball-milling Time is 200min, obtains the Graphene/[Ca of modification
0.35mg
0.16al
0.49(OH)
2] (NO
3)
0.490.5H
2o composition.Get its 10g to join in 90g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 2.5g and hydroxy silicon oil 3.5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv7.5h, corrosion depth 2.1mm, tensile strength 4.7MPa, elongation at break 589%, tear strength 8.1kN/m, alternating current breakdown intensity 24kV/mm.
Embodiment 5
By 0.023g graphene nanometer sheet, (thickness is 8nm, and length is 600nm, and specific surface area is 643m
2/ g) add in 26ml deionized water, the ultrasonic 60min of normal temperature, adds 5.27g calcium oxide, 6.41g magnesium sulfate, 17.32g Tai-Ace S 150 and 2.17g ferric sulfate, stir, put into ball mill wet-milling, drum's speed of rotation is 600r/min, and Ball-milling Time is 380min, then puts into baking oven and dries, put into ball mill dry grinding again, drum's speed of rotation is 550r/min, and Ball-milling Time is 160min, obtains Graphene/[Ca
0.47mg
0.13al
0.13fe
0.27(OH)
2] (SO
4)
0.22.5H
2o composition.Then add 4.2g vinyltriethoxysilane ball milling, drum's speed of rotation is 400r/min, and Ball-milling Time is 80min, obtains the Graphene/[Ca of modification
0.47mg
0.13al
0.13fe
0.27(OH)
2] (SO
4)
0.22.5H
2o composition.Get its 24g to join in 76g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 1.5g and hydroxy silicon oil 5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv7h, corrosion depth 1.6mm, tensile strength 6.2MPa, elongation at break 465%, tear strength 11.4kN/m, alternating current breakdown intensity 26kV/mm.
Embodiment 6
By 0.039g graphene nanometer sheet, (thickness is 15nm, and length is 1 μm, and specific surface area is 478m
2/ g) add in 34ml deionized water, the ultrasonic 60min of normal temperature, adds 17.95g magnesium nitrate, 28.76g aluminum nitrate, 4.71g iron nitrate and 3.62g cerous nitrate, stir, put into ball mill wet-milling, drum's speed of rotation is 750r/min, and Ball-milling Time is 350min, then puts into baking oven and dries, put into ball mill dry grinding again, drum's speed of rotation is 420r/min, and Ball-milling Time is 130min, obtains Graphene/[Mg
0.42al
0.46fe
0.07ce
0.05(OH)
2] (NO
3)
0.581.6H
2o composition.Then add 1.22g vinyl silane tri-butyl peroxy ball milling, drum's speed of rotation is 500r/min, and Ball-milling Time is 200min, obtains the Graphene/[Mg of modification
0.42al
0.46fe
0.07ce
0.05(OH)
2] (NO
3)
0.581.6H
2o composition.Get its 19g to join in 91g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.5g and hydroxy silicon oil 2.5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv8h, corrosion depth 2.5mm, tensile strength 5.7MPa, elongation at break 510%, tear strength 10.7kN/m, alternating current breakdown intensity 25kV/mm.
Embodiment 7
All the other are identical with embodiment 1, and the content except graphene nanometer sheet is 0.0115g.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv7h, corrosion depth 1.8mm, tensile strength 4.5MPa, elongation at break 690%, tear strength 7.3kN/m, alternating current breakdown intensity 23kV/mm.
Can be found by embodiment 1 contrast with embodiment 7, embodiment 7 by graphene nanometer sheet content further preferably, achieve the technique effect being significantly better than embodiment 1.
Embodiment 8
All the other are identical with embodiment 2, and the content except graphene nanometer sheet is 0.0143g.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kv11h, corrosion depth 1.6mm, tensile strength 7.2MPa, elongation at break 459%, tear strength 14.1kN/m, alternating current breakdown intensity 32kV/mm.
Can be found by embodiment 8 contrast with embodiment 2, embodiment 8 by graphene nanometer sheet content further preferably, achieve the technique effect being significantly better than embodiment 2.
Comparative example 1
8.97g calcium oxide is added in ball mill, 13.74g iron nitrate and 2.6g cerous nitrate, stir, put into ball mill wet-milling, drum's speed of rotation is 200r/min, Ball-milling Time is 660min, then put into baking oven to dry, then put into ball mill dry grinding, drum's speed of rotation is 700r/min, Ball-milling Time is 20min, obtains [Ca
0.8fe
0.17ce
0.03(OH)
2] (NO
3)
0.20.1H
2o layered hydroxide.Then add 5.1g vinyltriethoxysilane ball milling, drum's speed of rotation is 200r/min, and Ball-milling Time is 360min, obtains [the Ca of modification
0.8fe
0.17ce
0.03(OH)
2] (NO
3)
0.20.1H
2o layered hydroxide.Get its 5g to join in 95g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 1.5g and hydroxy silicon oil 3.5g, mixing slice.
Film after sulfuration after tested anti creepage trace can only pass through 2h under direct current 6.0kv, and corrosion depth reaches 3.6mm, tensile strength 2.9MPa, elongation at break 610%, tear strength 5.3kN/m, alternating current breakdown intensity 17kV/mm.
Can be found by embodiment 1 and comparative example 1, the product various aspects of performance of embodiment 1 is better than comparative example 1 all significantly, this explanation, in the present invention, adding of graphene nanometer sheet, on the basis of layered composite metal hydroxides, considerably enhance the various aspects of performance of product.
Comparative example 2
All the other are identical with embodiment 1, and the content except graphene nanometer sheet is 0.003g.
Film after sulfuration after tested anti creepage trace can only pass through 4h under direct current 6.0kv, and corrosion depth reaches 3.2mm, tensile strength 3.1MPa, elongation at break 604%, tear strength 5.9kN/m, alternating current breakdown intensity 18kV/mm.
Can be found by embodiment 1 and comparative example 2, very little, it is not enough to the various aspects of performance of remarkable improving product to the add-on of graphene nanometer sheet.
Comparative example 3
All the other are identical with embodiment 1, and the add-on except graphene nanometer sheet is 2g.
Can be found by embodiment 1 and comparative example 3, the add-on of graphene nanometer sheet is too many, and it is its insulating property of cracking significantly, cause it cannot be used for the preparation of direct-current ultra high voltage transmission line insulator device.
Film after sulfuration after tested anti creepage trace just destroys after 40min under direct current 6.0kv, and corrosion depth reaches 3.8mm, tensile strength 3.8MPa, elongation at break 647%, tear strength 7.5kN/m, alternating current breakdown intensity 12kV/mm.
Comparative example 4
Proportioning is identical with embodiment 1, but adopts method as described below to prepare:
By 0.0063g graphene nanometer sheet, (thickness is 1nm, and length is 100nm, and specific surface area is 1500m
2/ g) add in 20ml deionized water, the ultrasonic 60min of normal temperature, obtains dispersion liquid; In above-mentioned dispersion liquid, add 8.97g calcium oxide, 13.74g iron nitrate and 2.6g cerous nitrate, uniform stirring added urea after 10 ~ 30 minutes, backflow, by the suspension distilled water that obtains and ethanol repetitive scrubbing, dried.Then add 5.1g vinyltriethoxysilane ball milling, drum's speed of rotation is 200r/min, and Ball-milling Time is 360min, obtains the Graphene/[Ca of modification
0.8fe
0.17ce
0.03(OH)
2] (NO
3)
0.20.1H
2o composition.Get its 5g to join in 95g high-temperature silicon disulfide rubber, and add 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 1.5g and hydroxy silicon oil 3.5g, mixing slice.
Film after sulfuration after tested anti creepage trace reaches direct current 6.0kV6h, corrosion depth 2.2mm, tensile strength 2.5MPa, elongation at break 604%, tear strength 4.98kN/m, alternating current breakdown intensity 20kV/mm.
Comparative example 1 and comparative example 4 can find, the performance of each side of the product adopting the method for alternately ball milling of the present invention to obtain is better than adopting the method for comparative example 4 all significantly.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1., for a direct-current ultra high voltage insulation composition, it comprises following component:
(A) graphene nanometer sheet;
(B) layered composite metal hydroxides;
The volume of described graphene nanometer sheet is 0.025 ~ 0.1vol% of layered composite metal hydroxides volume.
2. direct-current ultra high voltage insulation composition as claimed in claim 1, it is characterized in that, the volume percent of described graphene nanometer sheet is 0.04 ~ 0.085vol%, preferably 0.045 ~ 0.07vol%;
Preferably, the thickness of described graphene nanometer sheet is 1 ~ 20nm, preferably 5 ~ 10nm; Length is 100nm ~ 20 μm, preferred 300nm ~ 5 μm; Specific surface area is 30 ~ 1500m
2/ g.
3. direct-current ultra high voltage insulation composition as claimed in claim 1 or 2, it is characterized in that, layered complex metal hydroxide has following general formula:
[M1
a 2+M2
b 2+M3
c 3+M4
d 3+(OH)
y]
x+(zA
n-)·vH
2O
Wherein M1 and M2 is divalent metal, and M1 includes but not limited to Ca
2+, Mg
2+, Zn
2+, Cu
2+, Co
2+or Ni
2+in any one, preferred Ca
2+, Mg
2+or Zn
2+in any one; M2 includes but not limited to Ca
2+, Mg
2+, Zn
2+, Cu
2+, Co
2+or Ni
2+in any one, preferred Co
2+, Ni
2+or Cu
2+in any one; M3 and M4 is trivalent metal cation, and M3 includes but not limited to Al
3+, Cr
3+, Fe
3+or Ce
3+in any one, preferred Al
3+or Fe
3+; M4 includes but not limited to Al
3+, Cr
3+, Fe
3+or Ce
3+in any one, preferred Cr
3+or Ce
3+;
A+b equals 1-x; C+d equals x, and wherein, x is (M3
3++ M4
3+)/(M1
2++ M2
2++ M3
3++ M4
3+) molar ratio, be 0.1 ~ 0.9, preferably 0.2 ~ 0.8, more preferably 0.5 ~ 0.7; Y is 1 ~ 6, preferably 2 ~ 4;
A
n-represent the tradable negatively charged ion of interlayer, include but not limited to nitrate radical, sulfate radical, lactate, amino acid, chlorion, carbonate, z is anion mol quantity, and n is negatively charged ion valence mumber, and wherein zn equals [2 (a+b)+3 (c+d)-y]; V is interlayer crystal water quantity, is 0.1 ~ 5, preferably 0.5 ~ 3.
4. the direct-current ultra high voltage insulation composition as described in one of claim 1-3, is characterized in that, described insulation composition also comprises (C) coupling agent;
Preferably, described coupling agent is silane coupling agent;
Preferably, (C) coupling agent is 1:5 ~ 1:70 with the weight ratio of (B) layered composite metal hydroxides, preferred 1:9 ~ 1:50, more preferably 1:12 ~ 1:45.
5. the direct-current ultra high voltage insulation composition as described in one of claim 1-4, is characterized in that, described insulation composition also comprises (D) solvent;
Preferably, (D) of the present invention solvent is 1:1.25 ~ 1:3 with the weight ratio of (B) layered composite metal hydroxides, preferred 1:1.5 ~ 1:2.5;
Preferably, described solvent is deionized water.
6. the preparation method for direct-current ultra high voltage insulation composition as described in one of claim 1-5, comprises the steps:
(I) graphene nanometer sheet is added ultrasonic disperse in solvent, then add the divalence and trivalent metal salt or oxide compound of preparing layered composite metal hydroxides, stir, then put into ball mill wet-milling, and post-drying;
(II) material obtained after oven dry is put into ball mill for dry grinding again;
Optionally, step (III) is carried out:
(III) coupling agent dry grinding is added.
7. method as claimed in claim 6, it is characterized in that, the temperature of step (I) ultrasonic disperse is 25 ~ 45 DEG C, and the time of ultrasonic disperse is 20 ~ 90min;
Preferably, the rotating speed of step (I) ball mill is 200 ~ 1000r/min, preferred 350r/min ~ 800r/min, and the wet-milling time is 200min ~ 660min, preferred 300min ~ 450min;
Preferably, step (II) drum's speed of rotation is 200 ~ 700r/min, preferred 350r/min ~ 600r/min, and the dry grinding time is 20min ~ 360min, preferred 30min ~ 240min;
Preferably, step (III) drum's speed of rotation is 200r/min ~ 500r/min, preferred 350r/min ~ 450r/min, and Ball-milling Time is 20min ~ 360min, preferred 30min ~ 240min.
8. the purposes for direct-current ultra high voltage insulation composition as described in one of claim 1-5, it is for the preparation of direct-current ultra high voltage transmission line insulator device.
9., for a direct-current ultra high voltage insulating composite material, it is containing, for example the direct-current ultra high voltage insulation composition one of claim 1-5 Suo Shu and polymeric matrix.
10. insulating composite material as claimed in claim 9, it is characterized in that, the quality of described direct-current ultra high voltage insulation composition accounts for 5 ~ 30% of direct-current ultra high voltage insulation composition and polymer-based carbon weight summation;
Preferably, described polymeric matrix is the mixture of any one or at least two kinds in silicon rubber, epoxy resin, polyethylene or tetrafluoroethylene.
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