CN112261858B - Graphene composite material and preparation method and application thereof - Google Patents
Graphene composite material and preparation method and application thereof Download PDFInfo
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- CN112261858B CN112261858B CN202011096336.4A CN202011096336A CN112261858B CN 112261858 B CN112261858 B CN 112261858B CN 202011096336 A CN202011096336 A CN 202011096336A CN 112261858 B CN112261858 B CN 112261858B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 28
- 229940070527 tourmaline Drugs 0.000 claims abstract description 28
- 239000011032 tourmaline Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000010008 shearing Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011358 absorbing material Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 6
- 238000009830 intercalation Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention provides a graphene composite material, and a preparation method and application thereof. The preparation method comprises the following steps: adding graphite, tourmaline powder and metal salt into a reactor, introducing carbon dioxide, controlling the pressure and temperature in the reactor to enable the carbon dioxide to reach a supercritical condition, peeling by stirring and shearing, cooling and decompressing after peeling to obtain a compound after supercritical carbon dioxide peeling; heating the composite under inert protective gas, continuously introducing hydrogen and acetylene for reaction, and cooling after the reaction to obtain the graphene composite material. The graphene composite material obtained by the method has excellent electron conduction capability and wave absorbing effect; the preparation process of the invention is green and environment-friendly, and can realize industrial mass production.
Description
Technical Field
The application belongs to the technical field of materials, and relates to a graphene composite material and a preparation method and application thereof.
Background
The advent of radar and stealth aircraft has allowed wave absorbing materials to enter the field of view of people. In the 5G era, due to the requirement for high frequency and high speed communication, there is also a new need for electromagnetic shielding inside smart phones. At the same time, electromagnetic pollution and radiation are also increasingly receiving attention. Graphene has wide application in wave-absorbing materials due to light weight, excellent conductivity and chemical stability. But a more excellent wave-absorbing performance cannot be achieved due to a single dielectric loss.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide a preparation method of a graphene composite material; the invention also aims to provide the graphene composite material prepared by the preparation method; the invention also aims at providing application of the graphene composite material as a wave-absorbing material.
The aim of the invention is achieved by the following technical means:
in one aspect, the invention provides a method for preparing a graphene composite material, comprising the following steps:
adding graphite, tourmaline powder and metal salt into a reactor, introducing carbon dioxide, controlling the pressure and temperature in the reactor to enable the carbon dioxide to reach a supercritical condition, peeling by stirring and shearing, cooling and decompressing after peeling to obtain a compound after supercritical carbon dioxide peeling;
heating the composite under inert protective gas, continuously introducing hydrogen and acetylene for reaction, and cooling after the reaction to obtain the graphene composite material.
Because graphene is a traditional dielectric wave-absorbing material, a mechanism of electromagnetic wave loss with single dielectric loss cannot realize good electromagnetic wave absorption; therefore, the invention enables carbon dioxide to reach a supercritical condition based on a certain pressure and temperature, and utilizes supercritical carbon dioxide fluid to strip graphite and tourmaline, rapidly decompress and expand, strip the graphite and the tourmaline into a few layers, and realize intercalation of graphene sheets and tourmaline powder in the same reactor, wherein the dielectric properties of the tourmaline and the graphene are different, more different interfaces are introduced, interface polarization effect in the material is enhanced, and the intercalation of the stripped graphene and the tourmaline is realized; meanwhile, metal salt is uniformly dispersed between graphene and the tourmaline sheet, under the catalysis of metal, under the vapor deposition reaction of carbon source acetylene, the carbon source acetylene is cracked, carbon nanotubes are grown between the graphene and the tourmaline layer, the tourmaline sheet and the graphene sheet are connected with each other, a conductive bridge is increased, the conductivity of electrons between materials is further enhanced, the conduction and polarization relaxation of electromagnetic wave energy are promoted, and thus the wave absorbing performance is comprehensively improved; the preparation process of the invention is green and environment-friendly, and can realize industrial mass production.
In the method, the amount of carbon dioxide introduced is reasonably selected according to actual operation so as to ensure that the supercritical carbon dioxide stripping can be realized.
In the above method, preferably, the mass ratio of the graphite, tourmaline powder and metal salt is (70 to 90): (10-12): 1.
in the above method, preferably, the graphite includes block graphite and/or flake graphite, and the like.
In the above method, preferably, the tourmaline powder has a mesh number of 1000 to 2000 mesh.
In the above method, preferably, the metal salt may include one or more of ferric chloride, ferrous sulfate, nickel chloride, nickel acetate, nickel sulfate, and the like.
In the above method, preferably, the compound stripped by supercritical carbon dioxide is placed in a reactor, carbon dioxide is introduced again, the pressure and temperature in the reactor are controlled so that the carbon dioxide reaches supercritical conditions, and supercritical carbon dioxide stripping is repeated for 5 times; the time for each stripping is 0.5-1 h.
In the above method, the stirring and shearing speed is preferably 100 to 4000rpm.
In the above method, it is preferable that the reaction pressure in the reactor is 8 to 12MPa and the reaction temperature is 35 to 100℃when the supercritical carbon dioxide stripping is performed.
In the above method, preferably, the temperature of the composite is raised to 600-800 ℃ under the inert protective gas, and the temperature raising rate is 10 ℃/min.
In the above method, preferably, the inert shielding gas is argon gas, and the flow rate of the argon gas is 50-100 sccm.
In the above method, preferably, the flow rate of the introduced hydrogen is 10 to 30sccm, and the flow rate of the introduced acetylene is 30 to 70sccm.
In the above method, preferably, the reaction is carried out by continuously introducing hydrogen and acetylene for 10 to 60 minutes.
On the other hand, the invention also provides the graphene composite material prepared by the method.
In still another aspect, the invention further provides an application of the graphene composite material as a wave-absorbing material.
The invention has the beneficial effects that:
according to the invention, supercritical carbon dioxide fluid is adopted to strip graphite and tourmaline, rapid decompression and expansion are realized, intercalation of the stripped graphene and tourmaline is realized, meanwhile, metal salt is uniformly dispersed between the graphene and the tourmaline sheet, carbon nano tubes grow between the graphene and the tourmaline sheet under the vapor deposition reaction of carbon source acetylene through the catalysis of metal, and the graphene sheet are mutually connected, so that the obtained graphene composite material has excellent electron conduction capability and wave absorption effect; the preparation process of the invention is green and environment-friendly, and can realize industrial mass production.
Drawings
Fig. 1 is a reflection loss experimental data diagram of electromagnetic parameter test of the graphene composite material prepared in embodiment 1 of the present invention through a vector network analyzer.
Fig. 2 is a graph of experimental data of reflection loss of the graphene material prepared in comparative example 1 according to the present invention, which is tested for electromagnetic parameters by a vector network analyzer.
Fig. 3 is a graph of experimental data of reflection loss of the graphene composite material prepared in comparative example 2 according to the present invention, which is tested for electromagnetic parameters by a vector network analyzer.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
the embodiment provides a preparation method of a graphene composite material, which comprises the following steps:
adding 210g of crystalline flake graphite, 30g of tourmaline powder (with the mesh number of 1000-2000 meshes) and 3g of nickel chloride into a reactor, introducing carbon dioxide, controlling the pressure in the reactor to be 12MPa and the temperature to be 60 ℃ so that the carbon dioxide reaches a supercritical condition, stirring, shearing and stripping under the stirring speed condition of 500rpm, cooling and cooling after stripping for 1h, and rapidly decompressing to obtain a compound stripped by the supercritical carbon dioxide;
repeating the stripping for 5 times (namely, putting the compound into a reactor, introducing carbon dioxide again, controlling the pressure in the reactor to be 12MPa and the temperature to be 60 ℃ so that the carbon dioxide reaches a supercritical condition, stirring, shearing and stripping at the stirring speed of 500rpm for 1h, repeating for 5 times), putting the obtained compound into a tube furnace, introducing argon (the gas flow rate is 100 sccm) as inert shielding gas, heating the tube furnace to 700 ℃ at 10 ℃/min, continuously introducing hydrogen (the gas flow rate is 20 sccm) and acetylene (the gas flow rate is 50 sccm) to react for 30min at 700 ℃, and then cooling to room temperature to obtain the graphene composite material with carbon nano tubes growing between graphene/tourmaline intercalation layers in situ, namely the graphene composite material prepared in the embodiment.
Example 2:
adding 270g of crystalline flake graphite, 33g of tourmaline powder (with the mesh number of 1000-2000 meshes) and 3g of ferrous sulfate into a reactor, introducing carbon dioxide, controlling the pressure in the reactor to be 12MPa and the temperature to be 60 ℃ so that the carbon dioxide reaches a supercritical condition, stirring, shearing and stripping under the stirring speed condition of 500rpm, cooling and cooling after stripping for 1h, and rapidly decompressing to obtain a compound stripped by the supercritical carbon dioxide;
repeating the stripping for 5 times (namely, putting the compound into a reactor, introducing carbon dioxide again, controlling the pressure in the reactor to be 12MPa and the temperature to be 60 ℃ so that the carbon dioxide reaches a supercritical condition, stirring, shearing and stripping at the stirring speed of 500rpm for 1h, repeating for 5 times), putting the obtained compound into a tube furnace, introducing argon (the gas flow rate is 100 sccm) as inert shielding gas, heating the tube furnace to 600 ℃ at 10 ℃/min, continuously introducing hydrogen (the gas flow rate is 20 sccm) and acetylene (the gas flow rate is 30 sccm) for reacting for 30min at 600 ℃, and then cooling to room temperature to obtain the graphene composite material with carbon nano tubes growing between graphene/tourmaline intercalation layers in situ, namely the graphene composite material prepared in the embodiment.
Example 3: wave absorbing performance test
The following wave-absorbing performance test was performed on the graphene composite material prepared in example 1:
weighing 320mg of paraffin (sizing agent), placing into a 100mL beaker, adding 3mL of n-hexane, placing into an ultrasonic pool for ultrasonic treatment for 15min, weighing 80mg of graphene composite material prepared in example 1, pouring into the beaker, continuing ultrasonic treatment for 10min, heating the uniformly mixed solution on a heating table, manually stirring until the n-hexane is completely evaporated, and pressing the obtained uniform mixture of the graphene composite material and the paraffin into a circular ring with the thickness of 1.5mm, the inner diameter of 3.04mm and the outer diameter of 7mm by using a die; and testing electromagnetic parameters by adopting a vector network analyzer, wherein the experimental result is shown in figure 1.
As can be seen from fig. 1, the wave absorbing performance of the graphene composite material of the invention is optimal, and the minimum reflection loss value is-29.5 dB.
Comparative example 1:
the graphene material was prepared by supercritical carbon dioxide exfoliation using only flake graphite, tourmaline powder and metal salt were not added, and other reaction conditions were the same as in example 1.
Experimental data of the electromagnetic parameter test performed by the vector network analyzer using the wave-absorbing performance test method of example 3 on the graphene material prepared in comparative example 1 are shown in fig. 2.
Comparative example 2:
the graphene composite material is prepared by supercritical carbon dioxide stripping of crystalline flake graphite and tourmaline powder, and metal salt is not added, and other reaction conditions are the same as in example 1.
Experimental data of electromagnetic parameter test by a vector network analyzer using the wave-absorbing performance test method of example 3 for the graphene composite material prepared in comparative example 2 are shown in fig. 3.
As can be seen from comparing fig. 1, fig. 2 and fig. 3, the wave absorbing performance of the graphene composite material prepared in the embodiment 1 of the present invention is optimal, the minimum reflection loss value is-29.5 dB, which is far better than those of comparative examples 1 and 2.
Claims (10)
1. The preparation method of the graphene composite material comprises the following steps:
adding graphite, tourmaline powder and metal salt into a reactor, introducing carbon dioxide, controlling the pressure and the temperature in the reactor to enable the carbon dioxide to reach a supercritical condition, peeling the graphite and the tourmaline powder by using supercritical carbon dioxide fluid through stirring and shearing, decompressing and expanding, peeling the graphite and the tourmaline powder into fewer layers, and realizing intercalation of graphene sheets and tourmaline powder in the same reactor to obtain a compound after supercritical carbon dioxide peeling;
heating the composite under inert protective gas, continuously introducing hydrogen and acetylene to react, cooling after the reaction to obtain the graphene composite material,
wherein the mass ratio of the graphite to the tourmaline powder to the metal salt is (70-90): (10-12): 1.
2. the method of claim 1, wherein the graphite comprises bulk graphite or flake graphite.
3. The method according to claim 1 or 2, wherein the tourmaline powder has a mesh number of 1000 to 2000 mesh.
4. The method of claim 1 or 2, wherein the metal salt comprises one or more of ferric chloride, ferrous sulfate, nickel chloride, nickel acetate, and nickel sulfate.
5. The method according to claim 1 or 2, wherein the stirring and shearing speed is 100 to 4000rpm.
6. The method of claim 1, wherein the supercritical carbon dioxide stripped composite is placed in a reactor, carbon dioxide is again introduced, the pressure and temperature in the reactor are controlled so that the carbon dioxide reaches supercritical conditions, and supercritical carbon dioxide stripping is repeated 5 times; the time for each stripping is 0.5-1 h.
7. The process according to claim 1 or 6, wherein the pressure in the reactor is 8-12 MPa and the temperature is 35-100 ℃.
8. The method of claim 1, wherein the compound is continuously fed with hydrogen and acetylene under inert protective gas, the temperature is 600-800 ℃, and the temperature rising rate is 10 ℃/min;
the inert shielding gas is argon, and the flow rate of the argon is 50-100 sccm;
the flow rate of the introduced hydrogen is 10-30 sccm, and the flow rate of the introduced acetylene is 30-70 sccm;
continuously introducing hydrogen and acetylene for reaction for 10-60 min.
9. The graphene composite material prepared by the method of any one of claims 1 to 8.
10. The use of the graphene composite material of claim 9 as a wave absorbing material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795613A (en) * | 2011-05-27 | 2012-11-28 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| CN103706337A (en) * | 2013-12-30 | 2014-04-09 | 成都纺织高等专科学校 | Formaldehyde-removal nano compound and preparation method thereof |
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| CN102515155B (en) * | 2012-01-05 | 2014-01-01 | 上海交通大学 | A method for supercritical carbon dioxide exfoliation to prepare large-scale graphene |
| CN103241721B (en) * | 2013-05-13 | 2014-12-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene/carbon nanotube composite system |
| US10081551B2 (en) * | 2016-07-15 | 2018-09-25 | Nanotek Instruments, Inc. | Supercritical fluid process for producing graphene from coke or coal |
| CN108192092B (en) * | 2017-12-30 | 2019-06-25 | 常州恒利宝纳米新材料科技有限公司 | A kind of graphene oxide, tourmaline powder, polyamide 6 composite material and preparation method thereof |
| CN108298530A (en) * | 2018-01-17 | 2018-07-20 | 中国石油大学(北京) | A kind of form the few-layer graphene alkene and the preparation method and application thereof |
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | A kind of supercritical carbon dioxide fluid preparation method and application of graphite/graphene composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795613A (en) * | 2011-05-27 | 2012-11-28 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| CN103706337A (en) * | 2013-12-30 | 2014-04-09 | 成都纺织高等专科学校 | Formaldehyde-removal nano compound and preparation method thereof |
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