CN116333414A - Nano zinc oxide-polypropylene based composite material, film and preparation method - Google Patents
Nano zinc oxide-polypropylene based composite material, film and preparation method Download PDFInfo
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- CN116333414A CN116333414A CN202211634894.0A CN202211634894A CN116333414A CN 116333414 A CN116333414 A CN 116333414A CN 202211634894 A CN202211634894 A CN 202211634894A CN 116333414 A CN116333414 A CN 116333414A
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- -1 zinc oxide-polypropylene Chemical group 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 214
- 239000011787 zinc oxide Substances 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 68
- 239000004743 Polypropylene Substances 0.000 claims abstract description 53
- 229920001155 polypropylene Polymers 0.000 claims abstract description 53
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 52
- 229920001721 polyimide Polymers 0.000 claims description 67
- 238000001035 drying Methods 0.000 claims description 34
- 238000007873 sieving Methods 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 238000011221 initial treatment Methods 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- 229910002113 barium titanate Inorganic materials 0.000 claims description 11
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 229910001923 silver oxide Inorganic materials 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 15
- 238000004146 energy storage Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 11
- 238000004381 surface treatment Methods 0.000 abstract description 11
- 239000010954 inorganic particle Substances 0.000 abstract description 10
- 230000005684 electric field Effects 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 239000011258 core-shell material Substances 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000002114 nanocomposite Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention provides a nano zinc oxide-polypropylene based composite material, a film and a preparation method thereof, wherein the nano zinc oxide-polypropylene based composite material comprises the following components in parts by weight: 7.5 to 22.5 parts of nano zinc oxide pretreatment particles, 38.75 to 46.25 parts of maleic anhydride grafted polypropylene and 38.75 to 46.25 parts of polypropylene. In the invention, the nano titanium dioxide filler after surface treatment is filled, the compatibility of inorganic particles and a matrix material is regulated and controlled, and the electrical property is improved; the nano particles are subjected to surface treatment, so that the compatibility of the inorganic particles and the organic matrix is increased, the structural optimization of the inorganic particles can be realized, the aggregation of the particles is reduced, the composite material with core-shell structure characteristics is formed by grafting polypropylene with maleic anhydride, the degree of electric field distortion of the inorganic particles and the matrix due to the large dielectric constant difference is optimized, the breakdown field intensity of the material is further improved, and the energy storage density of the material is further improved.
Description
Technical Field
The invention relates to the technical field of power equipment materials, in particular to a nano zinc oxide-polypropylene based composite material, a film and a preparation method thereof.
Background
With the development of the power capacitor towards light weight and miniaturization, the dielectric material with high energy storage density has wide application prospect in the field of capacitors, wherein the core-shell structure nano composite dielectric material is widely focused due to the excellent energy storage characteristic. Polypropylene (PP) is the main material of the commercial film capacitor at present because of its advantages of high breakdown field strength, low material loss, low cost, excellent mechanical properties, etc. For linear electrical materials such as PP, the maximum energy storage density Umax can be visually represented as:
wherein ε 0 For vacuum dielectric constant, ε r Is of relative dielectric constant, E b Is the breakdown field strength of the dielectric material.
From the above formula, it is known that increasing the relative dielectric constant and breakdown field strength of the material is an important way to improve the energy storage density of the material. Research shows that the addition of nanofillers to polymers is an effective means of regulating energy storage characteristics, so that the nanocomposite is considered as one of potential ideal capacitor energy storage materials and has wide application prospects. In order to improve the breakdown field strength, a large amount of inorganic nano particles with good insulating property and high compressive strength are selected as fillers, and although the breakdown strength of the prepared nano composite material is improved, the energy density of the nano composite material is limited to a lower level due to the excessively low dielectric constant (2.2) of PP from the aspect of engineering application, so that the nano composite material becomes a great obstacle for developing a high energy storage density capacitor.
Disclosure of Invention
In view of the above, the invention provides a nano zinc oxide-polypropylene based composite material, a film and a preparation method thereof, which aim to solve the problem of low energy storage density of the conventional capacitor polypropylene dielectric material.
In one aspect, the invention provides a polypropylene-based composite material, which comprises the following components in parts by weight: 7.5 to 22.5 parts of nano zinc oxide pretreatment particles, 38.75 to 46.25 parts of maleic anhydride grafted polypropylene and 38.75 to 46.25 parts of polypropylene.
Further, in the polypropylene-based composite material, the nano zinc oxide pretreatment particles comprise the following components in parts by weight: 90-95 parts of nano zinc oxide, 1-3 parts of nano zirconium dioxide, 0.5-2 parts of micron-sized barium titanate, 0.3-0.8 part of nano silver oxide and 0.3-0.8 part of nano manganese dioxide.
On the other hand, the invention also provides a preparation method of the polypropylene-based composite material, which comprises the following steps: step 1, sequentially performing initial treatment and surface modification treatment on a nano zinc oxide raw material to obtain zinc oxide pretreatment particles;
and 3, mixing the nano zinc oxide-maleic anhydride grafted polypropylene master batch, polypropylene and the rest maleic anhydride grafted polypropylene in the formula, adding a proper amount of antioxidant, and melt blending for a period of time at a second preset temperature to obtain the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite.
Further, in the preparation method of the polypropylene-based composite material, in the step 1, the initial treatment of the zinc oxide includes the following steps:
ball milling the nano zinc oxide raw material for 12-24 hours, drying and sieving to obtain the initially treated nano zinc oxide raw material;
mixing the initially treated nano zinc oxide raw material with nano zirconium dioxide, nano silicon dioxide, micron barium titanate, nano silver oxide and nano manganese dioxide according to the proportion, performing ball milling, drying and sieving to obtain first powder;
sintering the first powder for a period of time at 1100-1300 ℃ to obtain second powder;
and ball milling the second powder in alcohol for a period of time, and then drying and sieving to obtain nano zinc oxide particles.
Further, in the preparation method of the polypropylene-based composite material, the surface modification treatment of the zinc oxide comprises:
dispersing the nano zinc oxide particles obtained after the initial treatment in hydrogen peroxide solution, condensing and refluxing for 4-8 hours at 80-105 ℃, and then cleaning, drying and sieving to obtain first zinc oxide particles;
dispersing the first zinc oxide particles in a xylene solution, adding a proper amount of silane coupling agent, heating for a period of time in an inert gas atmosphere at 80-100 ℃, and then cleaning, drying and sieving to obtain second zinc oxide particles;
and (3) placing the second zinc oxide particles in a vacuum degree environment with the temperature of 150 ℃ and the pressure of 100kPa, and drying to obtain the nano zinc oxide modified particles.
Further, in the above method for preparing a polypropylene-based composite material, in the step 3, the first preset temperature is 180 to 200 ℃.
Further, in the above method for preparing a polypropylene-based composite material, in the step 3, the second preset temperature is 180-200 ℃.
The invention also provides a preparation method of the composite film containing the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material, which is characterized by comprising the following steps: cutting out a plurality of holes on the first polyimide film;
placing a second polyimide film at the bottom of the first polyimide film, placing a proper amount of nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material in the holes of the first polyimide film, and then placing a third polyimide film above the first polyimide film to package the third polyimide film;
and carrying out hot pressing treatment on each packaged polyimide film layer to obtain a composite film containing the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material.
Further, in the preparation method of the polypropylene-based composite material, the weight of the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material placed in the holes of the first polyimide film is 0.2-0.4g.
Further, in the preparation method of the polypropylene-based composite material, the temperature of the packaged polyimide films is 150-200 ℃ and the pressure is 15-20MPa.
According to the invention, polypropylene/maleic anhydride grafted polypropylene is used as a matrix, and the zinc oxide nano filler subjected to surface treatment is filled, so that the crystallization characteristic of the composite material can be obviously improved, and the combination of the polypropylene and the maleic anhydride grafted polypropylene improves the arrangement regularity of molecular chain segments of the composite material, so that the crystallization characteristic of the composite material is more stable. In addition, the surface treatment is carried out on the nano particles, the compatibility of the inorganic particles and the organic matrix is increased, the structural optimization of the inorganic particles can be realized, the aggregation of the particles is reduced, the composite material with core-shell structure characteristics is formed by grafting polypropylene with maleic anhydride, the degree of electric field distortion of the inorganic particles and the matrix due to the huge difference of dielectric constants is optimized, the breakdown field intensity of the material is further improved, and the energy storage density of the material is further improved.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a flow chart of a preparation method of a nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material provided by an embodiment of the invention;
FIG. 2 (a) is a SEM image of the microscopic morphology characterization of polypropylene composites without doped nano zinc oxide; FIGS. 2 (b) to 2 (d) are SEM (scanning electron microscope) graphs for representing the microcosmic appearance of the nano zinc oxide-polypropylene based composite material doped with different percentage contents according to the embodiment of the invention;
FIG. 3 shows the electrical properties of the nano zinc oxide-polypropylene based composite material provided by the embodiment of the invention, and FIG. 3 (a) shows the dielectric constant and material loss spectrum diagram; FIG. 3 (b) is a Weibull distribution of DC breakdown of the composite;
FIG. 4 is an energy density diagram of a nano zinc oxide-polypropylene based composite material provided by an embodiment of the invention under a 200MV/m electric field.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
Referring to fig. 1, the nano zinc oxide-polypropylene based composite material according to the embodiment of the invention comprises the following components in parts by weight: 7.5 to 22.5 parts of nano zinc oxide pretreatment particles, 38.75 to 46.25 parts of maleic anhydride grafted polypropylene and 38.75 to 46.25 parts of polypropylene.
Wherein:
the nano zinc oxide pretreatment particles comprise the following components in parts by weight: 90-95 parts of nano zinc oxide, 1-3 parts of nano zirconium dioxide, 0.5-2 parts of micron-sized barium titanate, 0.3-0.8 part of micron-sized silver oxide and 0.3-0.8 part of nano manganese dioxide; preferably, the nano zinc oxide pretreatment particles comprise the following components in parts by weight: 95 parts of nano zinc oxide, 1.5 parts of nano zirconium dioxide, 1.5 parts of nano titanium dioxide, 1 part of micron barium titanate, 0.5 part of nano silver oxide and 0.5 part of nano manganese dioxide. The particle size of the nano zinc oxide is preferably 50+/-20 nm, the particle size of the rest nano particles is smaller than 100nm, and the particle size of the micro particles is smaller than 100 mu m.
The maleic anhydride grafted polypropylene in this example was purchased from 21E830 grafted polypropylene, duPont, U.S.A.
The invention also provides a preparation method of the polypropylene-based composite material, which comprises the following steps:
and step 1, sequentially carrying out initial treatment and surface modification treatment on the zinc oxide raw material to obtain zinc oxide pretreatment particles.
In specific implementation, the initial treatment of the zinc oxide raw material comprises the following steps:
and 1a, ball milling the nano zinc oxide raw material for 12-24 hours, drying and sieving to obtain the nano zinc oxide raw material after initial treatment. In the ball milling process, nano zinc oxide can be added into absolute ethyl alcohol, wherein the absolute ethyl alcohol is selected as an impregnating agent. The rotational speed during ball milling may be 200-400 rpm, preferably 300 rpm.
Step 1b, mixing the initially treated nano zinc oxide raw material with nano zirconium dioxide, nano silicon dioxide, micron barium titanate, nano silver oxide and nano manganese dioxide according to the proportion, performing ball milling, drying and sieving to obtain first powder. In the step, a small amount of nano-scale zirconium dioxide, nano-scale silicon dioxide, micro-scale barium titanate, nano-scale silver oxide and nano-scale manganese dioxide are added so as to treat the nano-scale zinc oxide raw material, improve the crystal structure in the sintering process and facilitate the improvement of the potential gradient by the subsequent filler. In the step, deionized water can be used as a dispersion medium, zirconium balls are used as grinding media, the ball milling speed is 350 revolutions per minute, and the ball milling time is 10-14 hours, preferably 12 hours.
And step 1c, sintering the first powder for a period of time at 1100-1300 ℃ to obtain second powder. The sintering time may be 2-4 hours. After sintering, the crystal structure of the particles is improved, thereby realizing the pretreatment of the nano titanium dioxide filler
And step 1d, ball milling the second powder in alcohol for a period of time, and then drying and sieving to obtain the nano zinc oxide initial treatment particles. The ball milling time can be 12-24 hours. And absolute ethyl alcohol is used, so that the ball milling time is long, and the powder after the powder is contracted and agglomerated in the sintering process is sufficiently crushed, so that the nano-grade particles are obtained.
The surface modification treatment of zinc oxide comprises the following steps:
and 1a', dispersing the nano zinc oxide initial treatment particles in hydrogen peroxide solution, condensing and refluxing for 4-8 hours at 80-105 ℃, and then cleaning, drying and sieving to obtain first zinc oxide particles. The step adopts hydrogen peroxide to clean impurities and greasy dirt of the nano zinc oxide pretreated particles.
And 1b', dispersing the first zinc oxide particles in a xylene solution, adding a proper amount of silane coupling agent, heating for a period of time in an inert gas atmosphere at 80-100 ℃, and then cleaning, drying and sieving to obtain second zinc oxide particles. The heating time can be 12-24h. KH550 can be selected as the silane coupling agent. Xylene is selected to provide atmosphere for the surface treatment of the first titanium dioxide particles, and the sintered and crushed powder is subjected to surface treatment so as to form a core-shell structure conveniently; the two passes are to ensure nanoscale dimensions. The drying means may be lyophilization.
And step 1c', placing the second zinc oxide particles in a vacuum degree environment with the temperature of 150 ℃ and the vacuum degree of 100kPa, and drying to obtain the nano zinc oxide modified particles. The drying time may be from 10 to 14 hours, preferably 12 hours.
And 2, mixing the nano zinc oxide pretreatment particles obtained in the step 1 with a part of maleic anhydride grafted polypropylene, adding a proper amount of antioxidant, and carrying out melt blending for a period of time at a first preset temperature to obtain the nano zinc oxide-maleic anhydride grafted polypropylene master batch.
Specifically, nano titanium dioxide pretreatment particles, maleic anhydride grafted polypropylene and a proper amount of antioxidant are added into a torque rheometer for melt blending. The maleic anhydride grafted polypropylene was added in two portions to allow for adequate reaction. The antioxidant can be 1010, and the antioxidant accounts for 0.1wt% of the total weight of the raw materials.
And 3, mixing the nano zinc oxide-maleic anhydride grafted polypropylene master batch, polypropylene and the rest maleic anhydride grafted polypropylene in the formula, adding a proper amount of antioxidant, and melt blending for a period of time at a second preset temperature to obtain the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material.
Specifically, an antioxidant 1010 accounting for 0.1wt% of the weight of the raw material was added to prepare a modified polypropylene having a core-shell structure. The first preset temperature is 180-200 ℃; the second preset temperature is 180-200 ℃.
The invention also provides a preparation method of the composite film of the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material, which comprises the following steps:
step (1), cutting out a plurality of holes on a first polyimide film; the holes can be round holes, square holes, irregular holes and the like, and are preferably round holes, so that molten liquid can be uniformly dispersed in the hot pressing process conveniently, and a film with good particle dispersibility is formed. Step (2), placing a second polyimide film at the bottom of the first polyimide film, placing a proper amount of nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material in the holes of the first polyimide film, and then placing a third polyimide film above the first polyimide film to package the third polyimide film; the thickness of the first polyimide film, the second polyimide film, and the third polyimide film may be 100 μm.
In practice, the weight of the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material placed in the holes of the first polyimide film is 0.2-0.4g.
And (3) carrying out hot pressing treatment on each packaged polyimide film layer to obtain a composite film containing the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material.
In the step, the temperature of hot-pressing treatment is 150-200 ℃, preferably 190 ℃, on each layer of packaged polyimide film; the pressure is 15-20MPa, preferably 18MPa; the time of the autoclave is 10-20mins, preferably 18mins. In specific implementation, the packaged first polyimide film, second polyimide film and third polyimide film are placed in two square iron plates, and hot press treatment is carried out on the polyimide films by using a flat vulcanizing machine, the exhaust times are set to 15 times, and the exhaust time is set to 10s each time.
According to the invention, polypropylene/maleic anhydride grafted polypropylene is used as a matrix, and the zinc oxide nano filler subjected to surface treatment is filled, so that the crystallization characteristic of the composite material can be remarkably improved, on one hand, the introduced inorganic nano particles serve as crystal nuclei to promote crystallization, on the other hand, the introduction of the nano particles limits the growth space of the spherulites, the integrity and the size of the crystallization are damaged, and the number of spherulites is increased. The combination of the two improves the arrangement regularity of the molecular chain segments of the composite material, so that the crystallization characteristic of the composite material is more stable. In addition, the surface treatment is carried out on the nano particles, the compatibility of the inorganic particles and the organic matrix is increased, the structural optimization of the inorganic particles can be realized, the aggregation of the particles is reduced, the composite material with core-shell structure characteristics is formed by grafting polypropylene with maleic anhydride, the degree of electric field distortion of the inorganic particles and the matrix due to the huge difference of dielectric constants is optimized, and therefore the breakdown field intensity of the material is further improved.
However, when the inorganic filler in the nanocomposite dielectric material is reduced to a nano-scale, the interfacial area between the inorganic nanofiller and the polymer matrix is large in proportion, and the influence on the energy storage characteristics is large, and even becomes a key factor. Under the external electric field, the dielectric constant in the nano composite dielectric medium is inversely proportional to the local electric field intensity, and the larger the dielectric constant difference between the inorganic filler and the polymer matrix is, the more serious the local electric field intensity distortion at the interface is, so that the breakdown field intensity is reduced sharply, therefore, the ratio of the nano zinc oxide pretreatment particles to the maleic anhydride grafted polypropylene is controlled, the breakdown field intensity of the polypropylene-based composite material can be improved pertinently, and the energy storage density of the polypropylene dielectric material is improved.
The invention is described in detail below in several examples:
example 1
a. Ball milling 30g of nano zinc oxide in alcohol for 12 hours, drying and sieving to obtain 30g of initial treated nano zinc oxide raw material;
b. adding 28.4915g of nano zinc oxide obtained in the step a, 0.4465g of nano zirconium dioxide, 0.4472g of nano zinc oxide, 0.3112g of micron barium titanate, 0.1522g of nano silver oxide and 0.1518g of nano manganese dioxide into a ball milling tank, ball milling for 12h at a rotating speed of 350 r/min by taking deionized water as a dispersing medium and zirconium balls as a grinding medium, drying for 12h, and sieving to obtain 30g of first powder;
c. sintering 30g of the first powder for 3 hours at 1200 ℃ to obtain 25.3816g of second powder;
d. taking 25g of second powder, ball milling in alcohol for 12 hours, and then drying and sieving to obtain 25g of nano zinc oxide particles;
e. 15g of the nano zinc oxide is taken and dispersed in 100mL of hydrogen peroxide solution with the mass fraction of 35wt%, and is subjected to condensation reflux for 5 hours at 80 ℃ and then is cleaned, dried and sieved to obtain 15g of nano zinc oxide after surface treatment;
f. dispersing 15g of surface-treated nano zinc oxide particles in 300mL of xylene solution, adding 7.5g of silane coupling agent KH550, heating for 12 hours in a nitrogen atmosphere at 80 ℃, and then cleaning, drying and sieving to obtain 15g of surface-modified nano zinc oxide particles;
g. adding 15g of nano zinc oxide particles obtained in the step f and 35g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending for 10min at 180 ℃ to obtain 50g of nano zinc oxide-maleic anhydride grafted polypropylene master batch, wherein an antioxidant 1010 with the mass fraction of 0.1wt% is required to be added during the process;
h. 10g of nano zinc oxide-maleic anhydride grafted polypropylene master batch, 20g of polypropylene and 10g of maleic anhydride grafted polypropylene are added into a torque rheometer, and melt blending is carried out for 10 minutes at 180 ℃ to obtain 40g of nano zinc oxide-polypropylene based composite material, wherein the content of nano zinc oxide particles is 7.5wt%, and during the process, an antioxidant 1010 with the mass fraction of 0.1wt% is required to be added.
i. Cutting out a plurality of round holes with the diameter of 5cm on a first polyimide film with the thickness of 100 mu m by using a round cutter with the diameter of 50 mm;
j. placing a second polyimide film with the thickness of 100 mu m at the bottom of the first polyimide film, placing 0.2g of nano zinc oxide-polypropylene based composite material in a round hole of the first polyimide film, and then placing a third polyimide film with the thickness of 100 mu m above the first polyimide film for packaging;
k. and placing the packaged first polyimide film, second polyimide film and third polyimide film into two square iron plates, and performing hot pressing treatment on the polyimide films by using a flat vulcanizing machine to obtain the composite film containing the nano zinc oxide-polypropylene-based composite material, wherein the temperature of the flat vulcanizing machine is set to 150 ℃, the pressure is set to 15MPa, the treatment time is set to 20mins, the exhaust times are set to 15 times, and the exhaust time of each time is set to 10s.
Example 2
a. Ball milling 30g of nano zinc oxide in alcohol for 12 hours, drying and sieving to obtain 30g of initial treated nano zinc oxide raw material;
b. adding 28.4915g of nano zinc oxide, 0.4465g of nano zirconium dioxide, 0.4472g of nano zinc oxide, 0.3112g of micron barium titanate, 0.1522g of nano silver oxide and 0.1518g of nano manganese dioxide obtained in the step a into a ball milling tank, ball milling for 12h at a rotating speed of 350 r/min by taking deionized water as a dispersing medium and zirconium balls as a grinding medium, drying for 12h, and sieving to obtain 30g of first powder;
c. sintering 30g of the first powder for 3 hours at 1200 ℃ to obtain 25.3816g of second powder;
d. ball milling 25g of second powder in alcohol for 12h, drying and sieving to obtain 25g of nano zinc oxide particles;
e. dispersing 15g of nano zinc oxide in 100mL of hydrogen peroxide solution with the mass fraction of 35wt%, condensing and refluxing for 5 hours at 80 ℃, and then cleaning, drying and sieving to obtain 15g of nano zinc oxide after surface treatment;
f. dispersing 15g of surface-treated nano zinc oxide particles in 300mL of xylene solution, adding 7.5g of silane coupling agent KH550, heating for 12 hours in a nitrogen atmosphere at 80 ℃, and then cleaning, drying and sieving to obtain 15g of surface-modified nano zinc oxide particles;
g. adding 15g of nano zinc oxide particles obtained in the step f and 35g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending for 10min at 180 ℃ to obtain 50g of nano zinc oxide-maleic anhydride grafted polypropylene master batch, wherein an antioxidant 1010 with the mass fraction of 0.1wt% is required to be added during the process;
h. 20g of nano zinc oxide-maleic anhydride grafted polypropylene master batch, 10g of polypropylene and 10g of maleic anhydride grafted polypropylene are added into a torque rheometer, and melt blending is carried out for 10 minutes at the temperature of 180 ℃ to obtain 40g of nano zinc oxide-polypropylene based composite material, wherein the content of nano zinc oxide particles is 15wt%, and during the process, an antioxidant 1010 with the mass fraction of 0.1wt% is required to be added.
i. Cutting out a plurality of round holes with the diameter of 5cm on a first polyimide film with the thickness of 100 mu m by using a round cutter with the diameter of 50 mm;
j. placing a second polyimide film with the thickness of 100 mu m at the bottom of the first polyimide film, placing 0.2g of nano zinc oxide-polypropylene based composite material in a round hole of the first polyimide film, and then placing a third polyimide film with the thickness of 100 mu m above the first polyimide film for packaging;
k. and placing the packaged first polyimide film, second polyimide film and third polyimide film into two square iron plates, and performing hot pressing treatment on the polyimide films by using a flat vulcanizing machine to obtain the composite film containing the nano zinc oxide-polypropylene-based composite material, wherein the temperature of the flat vulcanizing machine is set to 190 ℃, the pressure is set to 15MPa, the treatment time is set to 15mins, the exhaust times are set to 15 times, and the exhaust time of each time is set to 10s.
Example 3
a. Ball milling 30g of nano zinc oxide in alcohol for 12 hours, drying and sieving to obtain 30g of initial treated nano zinc oxide raw material;
b. adding 28.4915g of nano zinc oxide, 0.4465g of nano zirconium dioxide, 0.4472g of nano zinc oxide, 0.3112g of micron barium titanate, 0.1522g of nano silver oxide and 0.1518g of nano manganese dioxide obtained in the step a into a ball milling tank, ball milling for 12h at a rotating speed of 350 r/min by taking deionized water as a dispersing medium and zirconium balls as a grinding medium, drying for 12h, and sieving to obtain 30g of first powder;
c. sintering 30g of the first powder for 3 hours at 1200 ℃ to obtain 25.3816g of second powder;
d. ball milling 25g of second powder in alcohol for 12h, drying and sieving to obtain 25g of nano zinc oxide particles;
e. dispersing 15g of nano zinc oxide in 100mL of hydrogen peroxide solution with the mass fraction of 35wt%, condensing and refluxing for 5 hours at 80 ℃, and then cleaning, drying and sieving to obtain 15g of nano zinc oxide after surface treatment;
f. dispersing 15g of surface-treated nano zinc oxide particles in 300mL of xylene solution, adding 7.5g of silane coupling agent KH550, heating for 12 hours in a nitrogen atmosphere at 80 ℃, and then cleaning, drying and sieving to obtain 15g of surface-modified nano zinc oxide particles;
g. adding 15g of nano zinc oxide particles obtained in the step f and 35g of maleic anhydride grafted polypropylene into a torque rheometer, and carrying out melt blending for 10min at 180 ℃ to obtain 50g of nano zinc oxide-maleic anhydride grafted polypropylene master batch, wherein an antioxidant 1010 with the mass fraction of 0.1wt% is required to be added during the process;
h. 30g of nano zinc oxide-maleic anhydride grafted polypropylene master batch, 5g of polypropylene and 5g of maleic anhydride grafted polypropylene are added into a torque rheometer, and melt blending is carried out for 10 minutes at the temperature of 180 ℃ to obtain 40g of nano zinc oxide-polypropylene based composite material, wherein the content of nano zinc oxide particles is 22.5wt%, and during the period, an antioxidant 1010 with the mass fraction of 0.1wt% is required to be added.
i. Cutting out a plurality of round holes with the diameter of 5cm on a first polyimide film with the thickness of 100 mu m by using a round cutter with the diameter of 50 mm;
j. placing a second polyimide film with the thickness of 100 mu m at the bottom of the first polyimide film, placing 0.2g of nano zinc oxide-polypropylene based composite material in a round hole of the first polyimide film, and then placing a third polyimide film with the thickness of 100 mu m above the first polyimide film for packaging;
k. and placing the packaged first polyimide film, second polyimide film and third polyimide film into two square iron plates, and performing hot pressing treatment on the polyimide films by using a flat vulcanizing machine to obtain the composite film containing the nano zinc oxide-polypropylene-based composite material, wherein the temperature of the flat vulcanizing machine is set to 150 ℃, the pressure is set to 18MPa, the treatment time is set to 15mins, the exhaust times are set to 15 times, and the exhaust time of each time is set to 10s.
The polypropylene-based composite materials prepared in examples 1-3 of the present invention were subjected to performance testing, and the results are shown in fig. 2-4:
fig. 2 (a) is a microscopic morphology characterization SEM image of a polypropylene composite without doped nano zinc oxide, fig. 2 (b) is a microscopic morphology characterization SEM image of a polypropylene composite doped with 7.5wt% nano zinc oxide, fig. 2 (c) is a microscopic morphology characterization SEM image of a polypropylene composite doped with 15wt% nano zinc oxide, and fig. 2 (d) is a microscopic morphology characterization SEM image of a polypropylene composite doped with 22.5wt% nano zinc oxide, as can be seen: in the preparation process of the composite material with different components, the phenomenon of particle agglomeration does not occur, and the dispersibility is good.
As can be seen from fig. 3 (a): the dielectric constant of the composite material shows monotonous rising trend along with the increase of the content of the nano zinc oxide particles, and when the content of the nano zinc oxide particles is 22.5 weight percent, the dielectric constant of the composite material is obviously increased compared with that of pure PP; as can be seen from fig. 3 (b): the introduction of nano zinc oxide particles can lead to a small decrease in breakdown field strength. Although the breakdown field strength of the composite material has a slight decrease trend, all samples maintain a high breakdown field strength above 350 MV/m. The composite material still retains sufficient margin and has a high pressure-resistant level.
As can be seen from fig. 4: under the same electric field intensity, the discharge energy density of the composite material has a monotonically rising trend along with the increase of the nano zinc oxide particles. When the content of the nano zinc oxide is 22.5wt%, the charging energy density and the discharging energy density of the composite material are respectively improved by 59.4% and 53.2% compared with pure PP.
In conclusion, the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material prepared by the embodiment of the invention has the advantages of high dielectric constant, higher breakdown field intensity, higher energy storage density than pure PP, and higher charge and discharge efficiency.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The polypropylene-based composite material is characterized by comprising the following components in parts by weight: 7.5 to 22.5 parts of nano zinc oxide pretreatment particles, 38.75 to 46.25 parts of maleic anhydride grafted polypropylene and 38.75 to 46.25 parts of polypropylene.
2. The polypropylene-based composite material according to claim 1, wherein the nano zinc oxide pretreatment particles comprise the following components in parts by weight: 90-95 parts of nano zinc oxide, 1-3 parts of nano zirconium dioxide, 0.5-2 parts of micron-sized barium titanate, 0.3-0.8 part of nano silver oxide and 0.3-0.8 part of nano manganese dioxide.
3. A method of producing a polypropylene-based composite material as claimed in claim 1 or 2, comprising the steps of:
step 1, sequentially performing initial treatment and surface modification treatment on a nano zinc oxide raw material to obtain zinc oxide pretreatment particles;
step 2, mixing the nano zinc oxide pretreatment particles with a part of maleic anhydride grafted polypropylene, adding a proper amount of antioxidant, and carrying out melt blending for a period of time at a first preset temperature to obtain a nano zinc oxide-maleic anhydride grafted polypropylene master batch;
and 3, mixing the nano zinc oxide-maleic anhydride grafted polypropylene master batch, polypropylene and the rest maleic anhydride grafted polypropylene in the formula, adding a proper amount of antioxidant, and melt blending for a period of time at a second preset temperature to obtain the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite.
4. A method of producing a polypropylene-based composite material according to claim 3, wherein in the step 1, the initial treatment of zinc oxide comprises the steps of:
ball milling the nano zinc oxide raw material for 12-24h, drying and sieving to obtain an initially treated nano zinc oxide raw material;
mixing the initially treated nano zinc oxide raw material with nano zirconium dioxide, nano silicon dioxide, micron barium titanate, nano silver oxide and nano manganese dioxide according to the proportion, performing ball milling, drying and sieving to obtain first powder;
sintering the first powder for a period of time at 1100-1300 ℃ to obtain second powder;
and (3) ball milling the second powder in alcohol for a period of time, and then drying and sieving to obtain the nano zinc oxide initial treatment particles.
5. A method of preparing a polypropylene-based composite material according to claim 3, wherein the surface modification treatment of zinc oxide comprises:
dispersing the nano zinc oxide particles obtained after the initial treatment in hydrogen peroxide solution, condensing and refluxing for 4-8 hours at 80-105 ℃, and then cleaning, drying and sieving to obtain first zinc oxide particles;
dispersing the first zinc oxide particles in a xylene solution, adding a proper amount of silane coupling agent, heating for a period of time in an inert gas atmosphere at 80-100 ℃, and then cleaning, drying and sieving to obtain second zinc oxide particles;
and (3) placing the second zinc oxide particles in a vacuum degree environment with the temperature of 150 ℃ and the pressure of 100kPa, and drying to obtain the nano zinc oxide modified particles.
6. The method for preparing a polypropylene-based composite material according to claim 3, wherein in the step 3, the first preset temperature is 180 to 200 ℃.
7. The method of producing a polypropylene-based composite material according to claim 3, wherein in the step 3, the second preset temperature is 180 to 200 ℃.
8. A method for preparing a composite film comprising the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material according to claim 1 or 2, comprising the steps of:
cutting out a plurality of holes on the first polyimide film;
placing a second polyimide film at the bottom of the first polyimide film, placing a proper amount of nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material in the holes of the first polyimide film, and then placing a third polyimide film above the first polyimide film to package the third polyimide film;
and carrying out hot pressing treatment on each packaged polyimide film layer to obtain a composite film containing the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material.
9. The method for preparing a polypropylene-based composite material according to claim 8, wherein the weight of the nano zinc oxide-polypropylene-maleic anhydride grafted polypropylene composite material placed in the round hole of the first polyimide film is 0.2-0.4g.
10. The method for preparing a polypropylene-based composite material according to claim 8, wherein the temperature of the heat pressing treatment of each layer of the packaged polyimide film is 150-200 ℃ and the pressure is 15-20MPa.
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| CN117264253B (en) * | 2023-09-27 | 2024-05-24 | 中国矿业大学 | Polypropylene composite dielectric material with high energy storage density and preparation method thereof |
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