CN114539525B - Neutron shielding film and preparation method and application thereof - Google Patents
Neutron shielding film and preparation method and application thereof Download PDFInfo
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- CN114539525B CN114539525B CN202210169769.0A CN202210169769A CN114539525B CN 114539525 B CN114539525 B CN 114539525B CN 202210169769 A CN202210169769 A CN 202210169769A CN 114539525 B CN114539525 B CN 114539525B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 122
- 229920001721 polyimide Polymers 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical group N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 65
- 229910052582 BN Inorganic materials 0.000 claims description 62
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 15
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 12
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical group B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000001282 organosilanes Chemical class 0.000 claims description 9
- 229910052580 B4C Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- PDYPRPVKBUOHDH-UHFFFAOYSA-N ditert-butyl(dichloro)silane Chemical compound CC(C)(C)[Si](Cl)(Cl)C(C)(C)C PDYPRPVKBUOHDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 abstract description 41
- 238000002444 silanisation Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
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- 239000000463 material Substances 0.000 description 13
- 239000005341 toughened glass Substances 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 229920005575 poly(amic acid) Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000009194 climbing Effects 0.000 description 5
- 239000007888 film coating Substances 0.000 description 5
- 238000009501 film coating Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- -1 Polyethylene Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
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- 239000004743 Polypropylene Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 230000035882 stress Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention discloses a neutron shielding film, a preparation method and application thereof, wherein the preparation process is as follows: respectively adding the heat conducting filler and the neutron shielding filler into ethanol, and performing ultrasonic treatment to obtain hydroxylated heat conducting filler and neutron shielding filler, and further preparing the heat conducting filler and neutron shielding filler with silanized surfaces; dispersing the heat conducting filler with silanized surface and the neutron shielding filler into a strong polar aprotic solvent, sequentially adding diamine monomer and dianhydride monomer, and stirring for in-situ polymerization to obtain polymer precursor liquid modified by the heat conducting filler and the neutron shielding filler; and preparing the obtained precursor liquid into a film, and performing high-temperature treatment after drying to obtain the polyimide film modified by the heat conducting filler and the neutron shielding filler. According to the invention, the heat conduction filler and the neutron shielding filler modified by the organic silanization reagent are added in the synthesis process of the polyimide film, so that the ultrathin polyimide neutron shielding film with good heat conduction performance is prepared.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer-based composite films, and relates to a neutron shielding film, a preparation method and application thereof.
Background
The neutron shielding material plays a vital role in the fields of nuclear power plants, nuclear medicine treatment and the like, and has wide application in the fields of nuclear waste treatment, neutron beam collimators, neutron traps, medical care and the like. With the development of science and technology, the polymer is more and more widely applied in the field of neutron shielding. The organic material has high hydrogen content, is the first choice of the fast neutron shielding material, and the common polymer used as the fast neutron shielding material comprises Polyethylene (PE), high Density Polyethylene (HDPE), polypropylene (PP), polyimide (PI) and the like, and the PI has extremely outstanding thermal stability, environmental aging resistance, chemical solvent resistance, mechanical strength and the like due to the imide ring contained in the main chain structural unit of the molecule, so the fast neutron shielding material is one of the polymer materials with optimal comprehensive properties at present, but has poor heat conducting property, so the material is easy to generate heat accumulation when being used for a long time or used in overload, and the material is easy to generate 'deterioration', such as thermal expansion, thermal degradation, heat accumulation and the like, thereby the service life of the material is reduced, and the use reliability of equipment is reduced. In some devices with high requirements on the average thickness of the thin film, such as medical devices, neutron beam collimators, neutron traps and the like, the volume of the devices is limited, wherein the average thickness of the sub-shielding film is required to be high, the average thickness of the PI thin film is only tens of micrometers, the neutron shielding performance of the PI thin film is poor, and the PI thin film can not be used almost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a neutron shielding film, and a preparation method and application thereof, thereby realizing that the heat conduction performance and the neutron shielding performance of the film material are effectively improved on the basis of ensuring the thickness of a PI film, prolonging the service life of the film material and improving the use reliability of equipment.
The invention is realized by the following technical scheme:
a preparation method of a neutron shielding film comprises the following steps:
s1: respectively adding the heat conducting filler and the neutron shielding filler into ethanol, performing ultrasonic treatment to obtain hydroxylated heat conducting filler and neutron shielding filler, and adding an organosilane reagent into the hydroxylated heat conducting filler and neutron shielding filler to obtain surface silanized heat conducting filler and neutron shielding filler;
S2: dispersing the surface silanized heat-conducting filler and the neutron shielding filler obtained in the step S1 into a strong polar aprotic solvent, sequentially adding diamine monomer and dianhydride monomer, and stirring for in-situ polymerization to obtain polymer precursor liquid modified by the heat-conducting filler and the neutron shielding filler;
S3: preparing a film from the heat-conducting filler and the neutron shielding filler modified polymer precursor liquid obtained in the step S2, and performing high-temperature treatment after drying to obtain a heat-conducting filler and neutron shielding filler modified polyimide film;
the heat conducting filler is any one of boron nitride, aluminum oxide and magnesium oxide;
The neutron shielding filler is any one of boron carbide, polyethylene and borax.
Preferably, the organosilane reagent is gamma-aminopropyl triethoxysilane or di-tert-butyldichlorosilane.
Preferably, the diamine monomer is one or a mixture of more than one of 4, 4-diaminodiphenyl ether, 4-diaminobiphenyl and p-phenylenediamine in any proportion.
Preferably, the dianhydride monomer is one or a mixture of more than one of pyromellitic anhydride, hexafluorodianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride in any proportion.
Preferably, the strong polar aprotic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide in any proportion.
Preferably, in the polymer precursor liquid modified by the heat conducting filler and the neutron shielding filler, the particle size of the heat conducting filler is 5-10 μm, and the adding amount of the heat conducting filler is 10-30% of the mass of the polymer precursor.
Preferably, in the polymer precursor liquid modified by the heat conducting filler and the neutron shielding filler, the particle size of the neutron shielding filler is 220 nm-350 nm, and the adding amount of the neutron shielding filler is 8% -15% of the mass of the polymer precursor.
Preferably, in the step S3, when the heat-conducting filler and the polymer precursor liquid modified by the neutron shielding filler obtained in the step S2 are made into a film, the first volume of the heat-conducting filler and the polymer precursor liquid modified by the neutron shielding filler are made into a first film, and after drying, the film forming process is repeated for several times until the average thickness of the dried film is 15 μm-200 μm.
A neutron shielding film, which has a thermal conductivity of 2 to 5W/(mK) and an average thickness of 10 to 100 μm, is produced by the above method.
The neutron shielding film is applied to neutron shielding.
Compared with the prior art, the invention has the following beneficial technical effects:
The preparation method of the neutron shielding film utilizes an organosilane reagent as a bridge reagent, so that the heat conducting filler and the neutron shielding filler effectively modify the polyimide film, the average thickness of the polyimide film is ensured, the heat conducting property of the polyimide neutron shielding film is effectively improved, the service life of the film is effectively prolonged, and the reliability of equipment is ensured. The invention creatively utilizes an organosilane reagent as a bridge, and adds the heat conduction filler and the neutron shielding filler modified by the organosilane reagent in the synthesis process of the polyimide film to prepare the ultrathin polyimide neutron shielding film with good heat conduction performance, and the polyimide film and the heat conduction filler and the neutron shielding filler form chemical bonding effect through the silylation reagent, so that the heat conduction filler and the neutron shielding filler are distributed in the polyimide film more uniformly, have stronger binding force and have more stable structure.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of BN/B 4 C/PI composite film in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of BN/B 4 C/PI composite film obtained in examples 1, 2, 3 of the invention;
FIG. 3 is a graph showing stress-strain curves of BN/PI composite films obtained in comparative examples 1, 2 and 3, B 4 C/PI composite film obtained in comparative example 4 and pure PI film obtained in comparative example 5 according to the present invention;
FIG. 4 is a graph showing stress strain curves of BN/B 4 C/PI composite films obtained in examples 1,2, and 3 of the present invention;
FIG. 5 is an infrared thermogram of BN/B 4 C/PI composite films obtained in examples 1,2, 3 of the present invention and of the individual PI films obtained in comparative example 5;
FIG. 6 is a graph showing the temperature change with time of BN/B 4 C/PI composite films obtained in examples 1,2, and 3 of the present invention and the individual PI films obtained in comparative example 5.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, the terms "comprising," including, "" containing, "" having, "or the like are intended to cover the meanings of" consisting of … … "and" consisting essentially of … …, "e.g.," A includes A "is intended to cover" A includes A and the other "and" A includes A only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention provides a preparation method of a neutron shielding film, which comprises the following steps:
S1: respectively adding a heat conducting filler and a neutron shielding filler into ethanol, carrying out ultrasonic treatment, carrying out hydroxylation treatment on the heat conducting filler and the neutron shielding filler to obtain a hydroxylated heat conducting filler and a hydroxylated neutron shielding filler, dropwise adding an organosilane reagent into a suspension of the hydroxylated heat conducting filler and the hydroxylated neutron shielding filler, stirring, drying and removing a solvent to obtain a heat conducting filler and a neutron shielding filler with silanized surfaces;
Wherein the heat conducting filler is any one of Boron Nitride (BN), aluminum oxide (Al 2O3) and magnesium oxide (MgO);
The neutron shielding filler is any one of boron carbide (B 4 C), polyethylene (PE) and borax.
The organosilane reagent is gamma-aminopropyl triethoxysilane (KH 550) or di-tert-butyldichlorosilane.
The hydroxylation process effectively improves the silanization efficiency, enhances the binding force between the silanization reagent and the heat conducting filler as well as the neutron shielding filler, and ensures that the binding force is firmer by combining the heat conducting filler and the neutron shielding filler in a chemical bonding mode.
S2: dispersing the surface silanized heat-conducting filler and the neutron shielding filler obtained in the step S1 into a strong polar aprotic solvent, slowly and sequentially adding a diamine monomer and a dianhydride monomer while stirring, and continuously stirring for in-situ polymerization until the solution viscosity becomes large and a pole climbing phenomenon occurs, so as to obtain a polymer precursor liquid modified by the heat-conducting filler and the neutron shielding filler, wherein the polymer is polyamide acid (PAA);
Wherein the strong polar aprotic solvent is one or a mixture of more of N, N-Dimethylformamide (DMF), N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide in any proportion.
The diamine monomer is one or a mixture of more of 4, 4-diaminodiphenyl ether, 4-diaminobiphenyl and p-phenylenediamine in any proportion.
The dianhydride monomer is one or a mixture of more of pyromellitic anhydride, hexafluorodianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride in any proportion.
The method comprises the steps of obtaining a heat conducting filler and a polymer precursor liquid modified by the neutron shielding filler, wherein the particle size of the heat conducting filler is 5-10 mu m, and the adding amount of the heat conducting filler is 10-30% of the mass of the polymer precursor. The particle size of the neutron shielding filler is 220 nm-350 nm, and the addition amount of the neutron shielding filler is 8% -15% of the mass of the polymer precursor.
S3: uniformly coating the heat-conducting filler and the neutron shielding filler modified polymer precursor liquid obtained in the step S2 on a toughened glass plate or stainless steel by using an automatic film coating machine, putting the toughened glass plate or stainless steel coated with the modified polyamic acid solution into an oven, preserving the temperature at 60 ℃ for 12-24 hours, and removing the solvent to obtain the modified polyamic acid composite film, wherein the coating and drying processes of the film can be repeated for a plurality of times until the average thickness of the modified polyamic acid composite film is 15-200 mu m. Then the modified polyamide acid composite film is peeled off from the glass according to the requirements, and is put into a high-temperature environment, and the heating and heat-preserving speed is controlled to imidize the modified polyamide acid composite film. The imidization process is that the obtained modified polyamide acid composite film is placed in a tube furnace or a muffle furnace, and is subjected to heat preservation for 0.5-2h at 120-170 ℃ and 0.5-2h at 230-270 ℃ and 0.5-2h at 300-350 ℃ in sequence, and naturally cooled to room temperature, so that the imidization process is completed, and the Polyimide (PI) film modified by the heat conducting filler and the neutron shielding filler is prepared. The thermal conductivity of the obtained neutron shielding film is 2-5W/(m.K), and the average thickness of the film is 10-100 μm.
Meanwhile, the invention protects the application of the prepared neutron shielding film in neutron shielding.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
A preparation method of neutron shielding film is shown in figure 1, which comprises the following steps:
S1: b 4 C and BN were each hydroxylated by sonication in ethanol. Then, dripping KH550 solution into the hydroxylated B 4 C and BN suspension, stirring, and drying to remove the solvent to obtain surface silanized B 4 C and BN;
S2: adding 0.3g of silanized B 4 C and 0.3g of silanized BN into a three-neck flask containing 10mL of DMF, sequentially adding 1.433 g of 4, 4-diaminodiphenyl ether, stirring to completely dissolve the 4, 4-diaminodiphenyl ether, continuously stirring, slowly adding 1.564g of pyromellitic anhydride, stirring until the viscosity of the solution becomes large, and climbing a rod to obtain BN/B 4 C/PAA solution, wherein BN accounts for 10% of PAA mass, and B 4 C accounts for 10% of PAA mass;
S3: taking out the mixed solution, uniformly coating the mixed solution on a toughened glass plate by using an automatic film coating machine, then placing the toughened glass plate coated with BN/B 4 C/PAA into a high-temperature oven, controlling the temperature rise and the heat preservation speed to imidize the toughened glass plate, wherein the imidization is to keep the temperature at 60 ℃ for 24 hours to remove the solvent, and then peeling off the dried BN/B 4 C/PAA composite film from the glass, wherein the average thickness of the BN/B 4 C/PAA composite film is 15 mu m. Then placing the materials in a tube furnace, sequentially preserving heat at 150 ℃ for 1h,250 ℃ for 1h,320 ℃ for 1h, naturally cooling to room temperature, and obtaining the neutron shielding film with heat conducting property. The thermal conductivity of the obtained neutron shielding film was 2W/(mK), and the average thickness of the film was 10. Mu.m.
The SEM image of the composite film is shown in fig. 2 (a), and it can be seen from the figure that BN and B 4 C are uniformly distributed on the surface of the PI film.
As can be seen from fig. 3, the addition of BN alone causes a decrease in the tensile strength of the PI film, and the higher the addition amount of BN, the more significant the decrease in the tensile strength of the PI film, i.e., the tensile strength is 2.5MPa and is reduced by 37.5% when the addition amount of BN is 30% as compared with the simple PI film. When the B 4 C is independently adopted to modify PI, the tensile strength of the film is 5MPa under the addition of 10% of B 4 C, which is improved by 25% compared with a pure PI film (4 MPa), the elongation at break is 22.5% and is improved by 12.5% compared with a pure PI film (10%). The addition of BN and B 4 C both enhances the elongation at break of the PI film, but the higher the addition amount of BN is, the lower the elongation at break of the PI film is.
The mechanical properties of the composite film prepared in this example are shown in fig. 4, and it can be seen that when the PI film is modified by BN and B 4 C together, the tensile strength (8 MPa) of the interlayer film is improved by 100% when the filling amounts of B 4 C and BN are 10% respectively in the PI/B 4 C/BN composite film.
The heat resistance and the heat conductivity of the composite film synthesized in the embodiment are shown in fig. 5 and 6, and when BN is added into the PI film, the heat conductivity of the film is effectively improved, so that the addition of BN can be known, and the temperature reaction time of the surface and the interior of the film is accelerated; meanwhile, as can be seen from fig. 5 and 6, the addition amount of BN should not be too high, which would affect the heat conductivity of the film. Meanwhile, the average thickness of the film is thinner, so that the temperature reaction speed is further accelerated, and the heat conduction performance of the film is further promoted.
The neutron shielding film prepared in this example had a thermal conductivity of 3W/(mK) and an average thickness of 30. Mu.m.
Example 2
S1: b 4 C and BN were hydroxylated by sonication in ethanol. Then, dripping KH550 solution into the hydroxylated B 4 C and BN suspension, stirring, and drying to remove the solvent to obtain surface silanized B 4 C and BN;
S2: adding 0.3g of silanized B 4 C and 0.6g of silanized BN into a three-neck flask containing 10mL of DMF, sequentially adding 1.433 g of 4, 4-diaminodiphenyl ether, stirring to completely dissolve the 4, 4-diaminodiphenyl ether, continuously stirring, slowly adding 1.564g of pyromellitic anhydride, stirring until the viscosity of the solution becomes large, and climbing a rod to obtain BN/B 4 C/PAA solution, wherein BN accounts for 20% of the mass of PAA, and B 4 C also accounts for 10% of the mass of PAA;
S3: taking out the mixed solution, uniformly coating the mixed solution on a toughened glass plate by using an automatic film coating machine, then placing the toughened glass plate coated with BN/B 4 C/PAA into a high-temperature oven, controlling the temperature rise and the heat preservation speed to imidize the toughened glass plate, wherein the imidization is to keep the temperature at 60 ℃ for 24 hours to remove the solvent, and then peeling the above BN/B 4 C/PAA composite film from the glass, wherein the thickness of the BN/B 4 C/PAA composite film is 55 mu m. Then placing the materials in a tube furnace, sequentially preserving heat at 150 ℃ for 1h,250 ℃ for 1h,320 ℃ for 1h, naturally cooling to room temperature, and obtaining the neutron shielding film with heat conducting property.
The neutron shielding film prepared in this example had a thermal conductivity of 3.4W/(mK) and an average thickness of 77. Mu.m.
The SEM image of the composite film prepared in this example is shown in fig. 2 (b), the strain test result is shown in fig. 4, and the heat resistance and heat conductivity of the composite film are shown in fig. 5 and 6.
Example 3
S1: b 4 C and BN were each hydroxylated by sonication in ethanol. Then, dripping KH550 solution into the hydroxylated B 4 C and BN suspension, stirring, and drying to remove the solvent to obtain surface silanized B 4 C and BN;
S2: adding 0.3g of silanized B 4 C and 0.9g of silanized BN into a three-neck flask containing 10mL of DMF, sequentially adding 1.433 g of 4, 4-diaminodiphenyl ether, stirring to completely dissolve the 4, 4-diaminodiphenyl ether, continuously stirring, slowly adding 1.564g of pyromellitic anhydride, stirring until the viscosity of the solution becomes large, and climbing a rod to obtain BN/B 4 C/PAA solution, wherein BN accounts for 30% of the PAA mass, and B 4 C also accounts for 10% of the PAA mass;
S3: taking out the mixed solution, uniformly coating the mixed solution on a toughened glass plate by using an automatic film coating machine, then placing the toughened glass plate coated with BN/B 4 C/PAA into a high-temperature oven, controlling the temperature rise and the heat preservation speed to imidize the toughened glass plate, wherein the imidization is to keep the temperature at 60 ℃ for 24 hours to remove the solvent, and then peeling the above BN/B 4 C/PAA composite film from the glass, wherein the thickness of the BN/B 4 C/PAA composite film is 130 mu m. And then placing the BN/B 4 C/PAA composite film into a tube furnace, sequentially carrying out heat preservation at 150 ℃ for 1h,250 ℃ for 1h,320 ℃ for 1h, naturally cooling to room temperature, and obtaining the neutron shielding film with heat conducting property.
The neutron shielding film prepared in this example had a thermal conductivity of 4W/(mK) and an average thickness of 103. Mu.m.
The SEM image of the composite film prepared in this example is shown in fig. 2 (c), the strain test result is shown in fig. 4, and the heat resistance and heat conductivity of the composite film are shown in fig. 5 and 6.
Comparative example 1
The difference from example 1 is that only the same mass of silylated BN was added and then 10% BN modified PI neutron shielding composite film, labeled pi+10% BN, was synthesized using the same mass of 4, 4-diaminodiphenyl ether and pyromellitic anhydride. The tensile strength and elongation at break of the film are shown in FIG. 3.
Comparative example 2
The difference from example 2 is that only the same mass of silylated BN was added, and then a 20% BN modified PI neutron shielding composite film, labeled pi+20% BN, was synthesized using the same mass of 4, 4-diaminodiphenyl ether and pyromellitic anhydride. The tensile strength and elongation at break of the film are shown in FIG. 3.
Comparative example 3
The difference from example 3 is that only the same mass of silylated BN was added and then a 30% BN modified PI neutron shielding composite film, labeled pi+30% BN, was synthesized using the same mass of 4, 4-diaminodiphenyl ether and pyromellitic anhydride. The tensile strength and elongation at break of the film are shown in FIG. 3.
Comparative example 4
The difference from example 1 was that only the same mass of silanized B 4 C was added, and then 10% B 4 C modified PI neutron shielding composite film, labeled pi+10% B 4 C, was synthesized using the same mass of 4, 4-diaminodiphenyl ether and pyromellitic anhydride. The tensile strength and elongation at break of the film are shown in FIG. 3.
Comparative example 5
The difference from example 1 is that no silylated B 4 C and BN were added and PI neutron shielding films were synthesized directly using the same mass of 4, 4-diaminodiphenyl ether and pyromellitic anhydride. The tensile strength and elongation at break of the film are shown in FIG. 3.
Example 4
S1: respectively adding boron nitride and boron carbide into ethanol, carrying out ultrasonic treatment, carrying out hydroxylation treatment on the boron nitride and the boron carbide to obtain hydroxylated boron nitride and boron carbide, dropwise adding gamma-aminopropyl triethoxysilane into the hydroxylated boron nitride and boron carbide suspension, stirring, drying and removing a solvent to obtain surface silanized boron nitride and boron carbide;
S2: dispersing the surface silanized boron nitride and boron carbide obtained in the step S1 into N, N-dimethylformamide, slowly and sequentially adding 4, 4-diaminodiphenyl ether and pyromellitic anhydride while stirring, and continuously stirring for in-situ polymerization until the solution viscosity becomes large and a pole climbing phenomenon occurs, so as to obtain the heat-conducting filler and the neutron shielding filler modified PAA;
Wherein the particle size of the heat conducting filler is 5 mu m, and the adding amount of the heat conducting filler is 10% of the mass of the polymer precursor. The particle size of the neutron shielding filler is 220nm, and the addition amount of the neutron shielding filler is 8% of the mass of the polymer precursor.
S3: uniformly coating the heat-conducting filler and the neutron shielding filler modified polymer precursor liquid obtained in the step S2 on a toughened glass plate or stainless steel by using an automatic film coating machine, putting the stainless steel coated with the modified polyamic acid solution into an oven, preserving heat for 12 hours at 60 ℃, and removing the solvent to obtain the modified polyamic acid composite film, wherein the coating and drying processes of the film can be repeated for a plurality of times until the average thickness of the modified polyamic acid composite film is 15 mu m. And then peeling the modified polyamide acid composite film from the stainless steel, putting the stainless steel into a high-temperature environment, and controlling the temperature rise and the heat preservation speed to imidize the polyamide acid composite film. The imidization process is that the obtained modified polyamide acid composite film is placed in a muffle furnace, and is subjected to heat preservation at 120 ℃ for 0.5h, at 230 ℃ for 0.5h and at 300 ℃ for 0.5h, and naturally cooled to room temperature, so that the imidization process is completed, and the Polyimide (PI) film modified by the heat conducting filler and the neutron shielding filler is prepared. The thermal conductivity of the obtained neutron shielding film was 2W/(mK), and the average thickness was 10. Mu.m.
Examples 5 to 8
The preparation method is the same as in example 4, and specific parameters and test results of the film materials are shown in table 1.
TABLE 1 results of Performance test of the composite film materials obtained by the parameters related to examples 5 to 8
Remarks:
In the table:
1. W Guide rail is the mass percentage of the addition amount of the heat-conducting filler to the mass of the polymer precursor;
2. W Shielding is the mass percent of the neutron shielding filler added to the polymer precursor.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the neutron shielding film is characterized by comprising the following steps of:
s1: respectively adding the heat conducting filler and the neutron shielding filler into ethanol, performing ultrasonic treatment to obtain hydroxylated heat conducting filler and neutron shielding filler, and adding an organosilane reagent into the hydroxylated heat conducting filler and neutron shielding filler to obtain surface silanized heat conducting filler and neutron shielding filler;
S2: dispersing the surface silanized heat-conducting filler and the neutron shielding filler obtained in the step S1 into a strong polar aprotic solvent, sequentially adding diamine monomer and dianhydride monomer, and stirring for in-situ polymerization to obtain polymer precursor liquid modified by the heat-conducting filler and the neutron shielding filler;
S3: preparing a film from the heat-conducting filler and the neutron shielding filler modified polymer precursor liquid obtained in the step S2, and performing high-temperature treatment after drying to obtain a heat-conducting filler and neutron shielding filler modified polyimide film;
The heat conducting filler is boron nitride;
the neutron shielding filler is boron carbide;
The particle size of the heat conducting filler is 5-10 mu m, and the adding amount of the heat conducting filler is 10-30% of the mass of the polymer precursor in the liquid of the polymer precursor modified by the heat conducting filler and the neutron shielding filler;
The particle size of the neutron shielding filler is 220-350 nm, and the addition amount of the neutron shielding filler is 8-15% of the mass of the polymer precursor;
in the step S3, when the heat-conducting filler and the polymer precursor liquid modified by the neutron shielding filler obtained in the step S2 are made into a film, the first volume of the heat-conducting filler and the polymer precursor liquid modified by the neutron shielding filler are made into a first film, and after drying, the film forming process is repeated for a plurality of times until the average thickness of the dried film is 15-200 μm.
2. The method for preparing a neutron shielding film according to claim 1, wherein the organosilane reagent is gamma-aminopropyl triethoxysilane or di-tert-butyldichlorosilane.
3. The method for preparing the neutron shielding film according to claim 1, wherein the diamine monomer is one or a mixture of more of 4, 4-diaminodiphenyl ether, 4-diaminobiphenyl and p-phenylenediamine in any proportion.
4. The method for preparing the neutron shielding film according to claim 1, wherein the dianhydride monomer is one or a mixture of more of pyromellitic anhydride, hexafluorodianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride in any proportion.
5. The method for preparing the neutron shielding film according to claim 1, wherein the strong polar aprotic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide in any proportion.
6. A neutron shielding film, characterized in that it is produced by the method of any one of claims 1 to 5, the neutron shielding film having a thermal conductivity of 2 to 5W/(m-K) and an average thickness of 10 μm to 100 μm.
7. The use of the neutron shielding film of claim 6 in neutron shielding.
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