CN107032325B - A kind of carbon nano tube composite wave-absorbing material and preparation method thereof - Google Patents
A kind of carbon nano tube composite wave-absorbing material and preparation method thereof Download PDFInfo
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- CN107032325B CN107032325B CN201710228474.5A CN201710228474A CN107032325B CN 107032325 B CN107032325 B CN 107032325B CN 201710228474 A CN201710228474 A CN 201710228474A CN 107032325 B CN107032325 B CN 107032325B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 51
- 239000011358 absorbing material Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 20
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 235000019441 ethanol Nutrition 0.000 claims abstract description 12
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- -1 rare earth compound Chemical class 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- NQLVCAVEDIGMMW-UHFFFAOYSA-N cyclopenta-1,3-diene;cyclopentane;nickel Chemical compound [Ni].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 NQLVCAVEDIGMMW-UHFFFAOYSA-N 0.000 claims abstract description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 4
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 238000001272 pressureless sintering Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003708 ampul Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910002420 LaOCl Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WVFDFRMEPUYSCI-UHFFFAOYSA-M Cl[La] Chemical compound Cl[La] WVFDFRMEPUYSCI-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 229910002545 FeCoNi Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B01J35/19—
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention belongs to microwave absorbing material technical field, it is related to a kind of carbon nano tube composite wave-absorbing material and preparation method thereof.The material is to be dissolved in the liquid carbon source containing additive that precursor solution is made by catalyst, then use and is added with iron particle and cobalt-nickel alloy particle, outer wall are attached with the composite wave-suction material of rare earth compound as matrix, in the inner wall of the carbon nanotube using carbon nanotube made of pressureless sintering method；The liquid carbon source is 1,2- dichloroethane solution, and additive is lanthanum nitrate, the ethyl alcohol also dissolved added with promotion lanthanum nitrate in liquid carbon source；The volume ratio 9:1 of 1,2- dichloroethane solution and ethyl alcohol, catalyst contain: the ferrocene of 33.93wt%, the cobaltocene of 33.19wt% and the dicyclopentadienyl nickel of 32.88wt%.Material of the present invention has the advantages that light weight, absorption frequency range is wide, absorbing property is significantly improved, environmental corrosion resisting is strong, has a wide range of application；The carbon nano-tube filled body purity is high obtained using the method for the invention, impurity are few.
Description
Technical field
The invention belongs to microwave absorbing material technical fields, and in particular to a kind of carbon nano tube composite wave-absorbing material and its system
Preparation Method.
Background technique
In traditional electromagnetic wave absorbent material, most widely used is ferrite, carbonyl iron dust, is inhaled although they have
The advantage that wave performance is strong, absorption band is wide, but density is high, the defect of quality weight, limits them and fills in invisbile plane, weapon
Standby upper application.As typical nano material, carbon nanotube not only has good electromagnetic wave absorption performance, also has density
Advantage low, light-weight, stability is high.By carbon nanotube combined with traditional absorbing material, it is prepared into novel carbon nanotube
Composite material all has great importance to the living environment for developing defense military, the protection mankind.
Transition metal element Fe can be obviously improved carbon as magnetic loss type absorbing material, after being filled into carbon nanotube and receive
The shortcomings that absorbing property of mitron, and document reported at present, generally existing Fe filling rate is high, Fe crystal form mixes,
Absorbing property need to be improved；The carbon nanotube of simple Fe filling, absorbing property room for promotion are limited.Use chemical vapor deposition
α-the Fe of (CVD, Chemical Vapor Deposition) method preparation or the filling of FeCoNi alloy particle and rare earth compound are attached
Carbon nanotube, to further increase the electro-magnetic wave absorption ability of material.Carbon nanotube composite is prepared using CVD method
Material has many advantages, since carbon nanotube has unique hollow structure, a loader can be considered, foreign substance
Be filled into the inside of pipe, it would not fall off easily, simultaneously because the protection of carbon-coating, exotic will not in air oxygen,
Moisture reacts, and expands the use scope of wave absorbing agent, and antiradar coatings have good environmental corrosion resisting performance, have more
Long service life.But carbon nanotube obtained still remains that purity is not high, and environmental stability is poor in the prior art, wave absorbtion
Can be poor the defects of.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of carbon nano tube composite wave-absorbing material and its preparations
Method.
The technical solution that the present invention solves the problems, such as is: providing a kind of carbon nano tube composite wave-absorbing material, the material is served as reasons
Catalyst, which is dissolved in the liquid carbon source containing additive, is made precursor solution, then use pressureless sintering method manufactured with
Carbon nanotube is matrix, in the inner wall of the carbon nanotube is attached with rare earth added with iron particle and cobalt-nickel alloy particle, outer wall
The composite wave-suction material of compound；The liquid carbon source is 1,2- dichloroethane solution, and the additive is lanthanum nitrate, the liquid
Also added with the ethyl alcohol for promoting lanthanum nitrate dissolution in state carbon source；The volume ratio 9:1 of 1, the 2- dichloroethane solution and ethyl alcohol, institute
Catalyst is stated to contain: the ferrocene of 33.93wt% (Weight%, weight percent), the cobaltocene of 33.19wt% and
The dicyclopentadienyl nickel of 32.88wt%.
Further, the rare earth compound is LaOCl (Lanthanum monochloride monoxide).
Further, in the precursor solution catalyst component ratio press substance meter are as follows: n (Fe): n (Co): n
(Ni)=1:1:1.
Further, the concentration of the precursor solution is less than 0.1g/mL (grams per milliliter).
Further, the component ratio of the ferrocene and lanthanum nitrate presses the meter of substance are as follows: n (Fe): n (La)=8:1.
The preparation method of the carbon nano tube composite wave-absorbing material, includes the following steps:
(1) catalytic component ratio n (Fe): n (Co): n (Ni)=1:1:1 is pressed, ferrocene, cobaltocene, dicyclopentadienyl nickel are dissolved
In the mixed solution of 1,2- dichloroethanes, ethyl alcohol that volume ratio is 9:1, lanthanum nitrate is added after mixing into mixed solution again,
Keep n (Fe): n (La)=8:1 that precursor solution is made after ultrasonic vibration is uniform；
(2) it by silicon wafer with acetone ultrasound ten minutes, then with EtOH Sonicate ten minutes, after thoroughly cleaning up, is blown with nitrogen
It is dry, then by position among the quartz ampoule of silicon wafer push-in tube furnace；
(3) it is passed through argon Ar toward the reaction chamber of quartz ampoule, holding flow velocity is 500sccm (Standard Cubic
Centimeter per Minute, standard milliliters per minute), continue five minutes, after draining the air in reaction chamber, to pre-add
Hot-zone is begun to warm up, a definite value for being maintained at the temperature of pre-add hot-zone within the scope of 220 DEG C~280 DEG C, to the anti-of tube furnace
Area is answered to be heated, a definite value for being maintained at reaction zone temperature within the scope of 750 DEG C~950 DEG C；
(4) argon Ar and hydrogen H are passed through2, keeping respective flow velocity is 1000sccm and 150sccm, ten minutes later, with note
Precursor solution is injected into pre-add hot-zone with 0.6ml/min (ml/min) speed and starts to react by emitter；
(5) reaction time after sixty minutes, stops injection precursor solution, closes hydrogen H2, keep argon Ar flow velocity be
Tube furnace is cooled to room temperature under argon Ar atmosphere by 350sccm；
(6) reaction chamber of quartz ampoule continues to be passed through argon Ar, and holding flow velocity is 500sccm, continues five minutes, drains reaction
Air in room, the reaction zone of tube furnace begin to warm to 750 DEG C, are sintered 3 hours at 750 DEG C；
(7) stop heating, keep argon Ar flow velocity constant, tube furnace is made to naturally cool to room temperature, collect on quartz boat
Product, the product are carbon nano tube composite wave-absorbing material, stop logical carrier gas.
Further, in step (3), so that the temperature of pre-add hot-zone is maintained at 250 DEG C, make the temperature of the reaction zone of tube furnace
It is maintained at 860 DEG C.
Further, in step (3), the temperature of the reaction zone of tube furnace is controlled by the first temperature controller, by the
The temperature of two temperature controllers control pre-add hot-zone.
Further, in step (4), the syringe is flow pump.
The invention has the benefit that
Compared to traditional absorbing material, there is quality using the carbon nano tube composite wave-absorbing material that technology of the invention obtains
Gently, the advantages of frequency range is wide, absorbing property is significantly improved is absorbed；The carbon nanotube obtained simultaneously using the method for the invention
Obturator purity is high, impurity are few；The absorbing material that especially present invention obtains has very strong environmental corrosion resisting performance, completely may be used
To be applied on the weaponrys such as ship, carrier-borne aircraft, have a wide range of application.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the Preparation equipment of carbon nano tube composite wave-absorbing material of the present invention；
Fig. 2 is TEM (transmission electron microscope) figure of carbon nano tube composite wave-absorbing material described in the embodiment of the present invention one；
Fig. 3 is the TEM figure of carbon nano tube composite wave-absorbing material described in the embodiment of the present invention two；
Fig. 4 is reflection loss figure of the carbon nano tube composite wave-absorbing material under different coating thickness in embodiment one；
Fig. 5 is reflection loss figure of the carbon nano tube composite wave-absorbing material under different coating thickness in embodiment two.
In figure: 1- precursor solution, 2- syringe, 3- reaction chamber, 4- pre-add hot-zone, 5- tube furnace, 6- the first temperature control
Device processed, 7- second temperature controller；
Arrow direction on the right side of Fig. 1 indicates argon Ar and hydrogen H2Be passed through direction；
Arrow meaning in Fig. 2 is that rare earth compound (LaOCl) nanoparticle is attached to carbon nanotube outer wall；Fig. 3 arrow
Meaning is that rare earth compound (LaOCl) nanocluster is attached to carbon nanotube outer wall；
CNT in Fig. 4 and Fig. 5 indicates carbon nanotube.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is further illustrated.
Embodiment one
As shown in Fig. 1, Fig. 2 and Fig. 4, a kind of carbon nano tube composite wave-absorbing material, the material is to be dissolved in by catalyst
Precursor solution 1 is made in liquid carbon source containing additive, then use that pressureless sintering method is manufactured to be with carbon nanotube
Matrix is attached with answering for rare earth compound added with iron particle and cobalt-nickel alloy particle, outer wall in the inner wall of the carbon nanotube
Close absorbing material；The liquid carbon source is 1,2- dichloroethane solution, and the additive is lanthanum nitrate, is gone back in the liquid carbon source
Added with the ethyl alcohol for promoting lanthanum nitrate dissolution；The volume ratio 9:1 of 1, the 2- dichloroethane solution and ethyl alcohol, the catalyst contain
Have: the ferrocene of 33.93wt%, the cobaltocene of 33.19wt% and the dicyclopentadienyl nickel of 32.88wt%.
The rare earth compound is LaOCl (Lanthanum monochloride monoxide).
The component ratio of catalyst presses the meter of substance in the precursor solution 1 are as follows: n (Fe): n (Co): n (Ni)=1:1:
1。
The concentration of the precursor solution 1 is less than 0.1g/mL.
The component ratio of the ferrocene and lanthanum nitrate presses the meter of substance are as follows: n (Fe): n (La)=8:1.
The preparation method of the carbon nano tube composite wave-absorbing material, includes the following steps:
(1) 0.41g (gram) ferrocene, 0.40g cobaltocene, 0.39g dicyclopentadienyl nickel are dissolved in 1, the 2- bis- of 54ml (milliliter)
In the mixed solution of chloroethanes and 6ml ethyl alcohol composition, 0.12g lanthanum nitrate is added after mixing into mixed solution again, is shaken through ultrasound
After swinging uniformly, precursor solution 1 is made；
(2) it by silicon wafer with acetone ultrasound ten minutes, then with EtOH Sonicate ten minutes, after thoroughly cleaning up, is blown with nitrogen
It is dry, then by position among the quartz ampoule of silicon wafer push-in tube furnace；
(3) it is passed through argon Ar toward the reaction chamber 3 of quartz ampoule, holding flow velocity is 500sccm, continues five minutes, drains reaction
After air in room 3, pre-add hot-zone 4 is begun to warm up, is kept by the temperature that second temperature controller 7 controls pre-add hot-zone 4
At 250 DEG C, the reaction zone of tube furnace 5 is heated, the temperature of the reaction zone of tube furnace 5 is controlled by the first temperature controller 6
Degree is maintained at 860 DEG C；
(4) argon Ar and hydrogen H are passed through2, keeping respective flow velocity is 1000sccm and 150sccm, ten minutes later, with note
Precursor solution 1 is injected into pre-add hot-zone 4 with 0.6ml/min speed and starts to react by emitter 2；
(5) reaction time after sixty minutes, stops injection precursor solution 1, closes hydrogen H2, keep argon Ar flow velocity be
Tube furnace 5 is cooled to room temperature under argon Ar atmosphere by 350sccm；
(6) reaction chamber 3 of quartz ampoule continues to be passed through argon Ar, and holding flow velocity is 500sccm, continues five minutes, drains anti-
The air in room 3 is answered, the reaction zone of tube furnace 5 begins to warm to 750 DEG C, is sintered 3 hours at 750 DEG C；
(7) stop heating, keep argon Ar flow velocity constant, tube furnace 5 is made to naturally cool to room temperature, collect on quartz boat
Carbon nano tube composite wave-absorbing material stops logical carrier gas, and phenetic analysis and crystal structure, tests its electromagnetic performance.
Wherein, in step (4), the syringe 2 is flow pump.
Embodiment two
As shown in Fig. 1, Fig. 3 and Fig. 5, in the present embodiment, the preparation method of the carbon nano tube composite wave-absorbing material
Step (1) are as follows: 0.82g ferrocene, 0.80g cobaltocene, 0.78g dicyclopentadienyl nickel are dissolved in 1, the 2- dichloroethanes and 6ml of 54ml
In the mixed solution of ethyl alcohol composition, 0.24g lanthanum nitrate is added after mixing into mixed solution again, after ultrasonic vibration is uniform, system
At precursor solution 1；
In addition to this, other content is the same as example 1.
Embodiment three
In the present embodiment, in (3), make to preheat the preparation method of the carbon nano tube composite wave-absorbing material the step of
The temperature in area 4 is maintained at 220 DEG C, heats to the reaction zone of tube furnace 5, and reaction zone temperature is made to be maintained at 750 DEG C.
In addition to this, other content is the same as example 1.
Example IV
In the present embodiment, in (3), make to preheat the preparation method of the carbon nano tube composite wave-absorbing material the step of
The temperature in area 4 is maintained at 280 DEG C, heats to the reaction zone of tube furnace 5, and reaction zone temperature is made to be maintained at 950 DEG C.
In addition to this, other content is the same as example 1.
Present invention is not limited to the embodiments described above, without departing substantially from substantive content of the present invention, art technology
Any deformation, improvement, the replacement that personnel are contemplated that each fall within protection scope of the present invention.
Claims (9)
1. a kind of carbon nano tube composite wave-absorbing material, which is characterized in that the material is to be dissolved in by catalyst containing additive
Liquid carbon source in precursor solution is made, then use pressureless sintering method it is manufactured using carbon nanotube as matrix, described
The inner wall of carbon nanotube is attached with the composite wave-suction material of rare earth compound added with iron particle and cobalt-nickel alloy particle, outer wall；
The liquid carbon source is 1,2- dichloroethane solution, and the additive is lanthanum nitrate, is also added with and promotes in the liquid carbon source
The ethyl alcohol of lanthanum nitrate dissolution；The volume ratio 9:1 of 1, the 2- dichloroethane solution and ethyl alcohol, the catalyst contain:
The ferrocene of 33.93wt%, the cobaltocene of 33.19wt% and the dicyclopentadienyl nickel of 32.88wt%.
2. carbon nano tube composite wave-absorbing material according to claim 1, which is characterized in that the rare earth compound is
LaOCl。
3. carbon nano tube composite wave-absorbing material according to claim 1, which is characterized in that be catalyzed in the precursor solution
The component ratio of agent presses the meter of substance: n (Fe): n (Co): n (Ni)=1:1:1.
4. carbon nano tube composite wave-absorbing material according to claim 1, which is characterized in that the concentration of the precursor solution
Less than 0.1g/mL.
5. carbon nano tube composite wave-absorbing material according to claim 1, which is characterized in that the ferrocene and lanthanum nitrate
Component ratio presses the meter of substance: n (Fe): n (La)=8:1.
6. the method for preparing the described in any item carbon nano tube composite wave-absorbing materials of claim 1-5, which is characterized in that including such as
Lower step:
(1) amount ratio n (Fe): n (Co): n (Ni)=1:1:1 of catalyst component species, ferrocene, cobaltocene, dicyclopentadienyl nickel is molten
Nitric acid is added in the mixed solution of 1,2- dichloroethanes, ethyl alcohol that volume ratio is 9:1 in solution into mixed solution again after mixing
Lanthanum keeps the component ratio of ferrocene and lanthanum nitrate to press the meter of substance: n (Fe): n (La)=8:1, after ultrasonic vibration is uniform,
Precursor solution is made；
(2) by silicon wafer with acetone ultrasound ten minutes, then with EtOH Sonicate ten minutes, after thoroughly cleaning up, with being dried with nitrogen, so
Afterwards by position among the quartz ampoule of silicon wafer push-in tube furnace；
(3) it is passed through argon Ar toward the reaction chamber of quartz ampoule, holding flow velocity is 500sccm, continues five minutes, drains in reaction chamber
After air, pre-add hot-zone is begun to warm up, a definite value for being maintained at the temperature of pre-add hot-zone within the scope of 220 DEG C~280 DEG C,
The reaction zone of tube furnace is heated, a definite value for being maintained at reaction zone temperature within the scope of 750 DEG C~950 DEG C；
(4) argon Ar and hydrogen H are passed through2, keeping respective flow velocity is that 1000sccm and 150sccm uses syringe ten minutes later
Precursor solution pre-add hot-zone is injected into 0.6ml/min speed to start to react；
(5) reaction time after sixty minutes, stops injection precursor solution, closes hydrogen H2, holding argon Ar flow velocity is 350sccm,
Tube furnace is cooled to room temperature under argon Ar atmosphere；
(6) reaction chamber of quartz ampoule continues to be passed through argon Ar, and holding flow velocity is 500sccm, continues five minutes, drains in reaction chamber
Air, the reaction zone of tube furnace begins to warm to 750 DEG C, is sintered 3 hours at 750 DEG C；
(7) stop heating, keep argon Ar flow velocity constant, tube furnace is made to naturally cool to room temperature, collect the product on quartz boat,
Stop logical carrier gas.
7. the preparation method of carbon nano tube composite wave-absorbing material according to claim 6, which is characterized in that in step (3),
So that the temperature of pre-add hot-zone is maintained at 250 DEG C, the temperature of the reaction zone of tube furnace is made to be maintained at 860 DEG C.
8. the preparation method of carbon nano tube composite wave-absorbing material according to claim 6 or 7, which is characterized in that step (3)
In, the temperature of the reaction zone of tube furnace is controlled by the first temperature controller, and pre-add hot-zone is controlled by second temperature controller
Temperature.
9. the preparation method of carbon nano tube composite wave-absorbing material according to claim 6, which is characterized in that in step (4),
The syringe is flow pump.
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