CN102010690A - Carbon nanotube composite material filled with ferrous sulfide, preparation method and application thereof - Google Patents
Carbon nanotube composite material filled with ferrous sulfide, preparation method and application thereof Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 96
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 96
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title abstract 7
- 239000000463 material Substances 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000012188 paraffin wax Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 123
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 76
- -1 carbon nano tube compound Chemical class 0.000 claims description 68
- 239000000377 silicon dioxide Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 44
- 229910001220 stainless steel Inorganic materials 0.000 claims description 41
- 239000010935 stainless steel Substances 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 229910052786 argon Inorganic materials 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 38
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 29
- 239000010453 quartz Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000004567 concrete Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000010504 bond cleavage reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000007017 scission Effects 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000010963 304 stainless steel Substances 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
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- 230000014509 gene expression Effects 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QQMBXJNYDBLJHH-UHFFFAOYSA-N [C].CSC Chemical compound [C].CSC QQMBXJNYDBLJHH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a carbon nanotube composite material filled with ferrous sulfide, a preparation method and an application thereof, in particular to a carbon nanotube composite material which is filled with the ferrous sulfide and has the advantages of adjustable electrical conductivity, light weight, good stability and stronger broadband microwave absorbability, a preparation method and an application thereof. The key point of the carbon nanotube composite material filled with the ferrous sulfide is as follows: the cavity of the carbon nanotube is provided with the ferrous sulfide, wherein, the molecular formula of the ferrous sulfide is Fe7S8. In the preparation method of the carbon nanotube composite material filled with the ferrous sulfide, the Fe7S8 in the cavity of the carbon nanotube is filled in situ during the growth process of the carbon nanotube. In the invention, the carbon nanotube composite material is taken as an electromagnetic wave absorbing material and an electromagnetic shielding material; and when in use, the carbon nanotube composite material is uniformly dispersed in paraffin wax or epoxy resin and then coated on the surface of an object requiring for being coated.
Description
Technical field
The present invention relates to the carbon nano tube compound material that a kind of iron sulphide is filled, belong to the inorganic nano composite material field; The invention still further relates to its preparation method and the application aspect microwave absorbing.
Background technology
Carbon nanotube has caused that with its particular structure and excellent performance global scientist pays close attention to closely and widely since being found, as its electric property, and magnetic performance, mechanical property is the focus that people study always.Carbon nanotube is in the successful use of aspects such as electronic sensor, battery material, transistor, nanodevice in recent years, impels people to study more on a large scale and prepares.Because there is confinement effect in the nanometer space of carbon nanotube, make the material that is filled in the carbon nanotube cavity inside can show with in the mutually different character of macroscopic body.Therefore scientists has been carried out a lot of researchs, and metal or its oxide material are filled in the carbon nanotube to obtain having the matrix material of specific function.At present the research report of the carbon nano tube compound material that metallic sulfide is filled seldom.Because metallic sulfide has special physicochemical character, and carbon nanotube is a kind of nano material of excellent performance, have characteristics such as the desired electroconductibility of preparation stealth material is adjustable, light weight, good stability, also having shown stronger wide-band microwave absorptive character, is that the ideal of preparation absorbing material is selected.Therefore the carbon nanotube of preparing the metallic sulfide filling will be a kind of matrix material with property.
At present the preparation carbon nano tube compound material method have multiple as: capillary completion method, solution chemistry method, arc discharge method, pyrolysis metallorganics method.But most methods exists shortcomings such as filling process is loaded down with trivial details, the complicated process of preparation filling ratio is low have limited the widespread adoption of the carbon nano tube compound material of filling.Traditional used catalyzer of preparation carbon nanotube is generally transition metal such as Fe, Co, Ni etc., these metal catalysts often are carried on some carriers, as magnesium oxide, porous silica, aluminum oxide etc., and the metal filled possibility of advancing carbon nanotube is very little, and the carbon nano tube compound material that particularly adopts iron sulphide to fill does not appear in the newspapers so far.
Summary of the invention
The purpose of this invention is to provide that a kind of electroconductibility is adjustable, light weight, good stability, and carbon nano tube compound material that the iron sulphide of stronger wide-band microwave absorptive character fills and preparation method thereof is arranged; Another object of the present invention provides the application of carbon nano tube compound material aspect microwave absorbing that described iron sulphide is filled.
The present invention finishes by following technical scheme, the carbon nano tube compound material that a kind of iron sulphide is filled, and this carbon nano tube compound material has iron sulphide in the inner chamber of carbon nanotube, and the molecular formula of wherein said iron sulphide is Fe
7S
8
In the carbon nano tube compound material that above-mentioned a kind of iron sulphide is filled, the preparation method of this carbon nano tube compound material is: the Fe in the carbon nanotube cavity
7S
8Original position is filled in the carbon nano tube growth process, and method is simple.
In the preparation method of the carbon nano tube compound material that above-mentioned iron sulphide is filled, the preparation of the carbon nano tube compound material that iron sulphide is filled may further comprise the steps:
(1) stainless steel substrates is cut into any size, cleans stand-by;
(2) above-mentioned stainless steel substrates is put into process furnace; Feed the air in argon gas or the nitrogen eliminating reaction chamber earlier, then process furnace is warming up to temperature of reaction, temperature of reaction is between 950～1200 ℃;
(3) dimethyl sulphide steam is fed reaction chamber and react, stop the dimethyl sulphide steam supply after reaction finishes, make process furnace be cooled to room temperature, the black deposit that forms on stainless steel substrates is carbon nano tube compound material.
In the preparation method of the carbon nano tube compound material that above-mentioned iron sulphide is filled, be catalyzer and substrate with the stainless steel substrates, with the dimethyl sulphide carbon source, feed hydrogen and argon gas, at high temperature carry out prepared in reaction.
In the preparation method of the carbon nano tube compound material that above-mentioned iron sulphide is filled, the preparation concrete steps of the carbon nano tube compound material that iron sulphide is filled are as follows:
(1) selected raw chemical material
Preparation carbon nano tube compound material required raw chemical material is carried out selected, and carries out the control of purity and precision:
Dimethyl sulphide: colourless liquid, purity 〉=99.0%;
Stainless steel substrates: adopt 304 stainless steel substrates, thickness≤0.2mm;
Dehydrated alcohol: colourless liquid, purity 〉=99.7%;
Deionized water: colourless liquid, purity 〉=99.7%;
Hydrochloric acid: colourless liquid, concentration 10.0～35.0%;
Argon gas: gas, purity 〉=99.9%;
Hydrogen: gas, purity 〉=99.99%;
(2) clean silica tube
With the inner and outer wall of tap water lavation, flushing silica tube, scrub the inwall of silica tube then with 500～1000ml deionized water, make its cleaning, clean two-port with dehydrated alcohol again, cleaning finishes to be placed on the platform dries, standby;
(3) clean quartz boat
Quartz boat is placed beaker, add deionized water 80～100ml, soak and jog beaker 4～6s, outwell deionized water; Add dehydrated alcohol 80～100ml then, be placed in the ultrasonic cleaner, ultrasonic cleaning 10～20min;
(4) drying treatment quartz boat
Place loft drier dry the taking-up of quartz boat after the ultrasonic cleaning, drying temperature is 100～150 ℃, and be 15～20min time of drying, takes out cooling, and is standby;
(5) clean stainless steel substrates
Stainless steel substrates is cut into suitable size (such as 1cm * 3cm), place beaker, to add hydrochloric acid 15～20ml, soaks 5～10min; Take out stainless steel substrates then and put into the beaker that fills 80～100ml dehydrated alcohol again, be placed in the ultrasonic cleaner, ultrasonic cleaning 10～20min, taking-up is dried, and is standby;
(6) handle stainless steel substrates
1. above-mentioned cleaned standby stainless steel substrates is placed quartz boat;
2. this quartz boat is put into the silica tube central section;
3. with the port shutoff of the silica tube left and right sides, left part connects argon gas and hydrogen pipe, and right part connects escape pipe;
4. open argon gas steel gas cylinder, flow is 100～200ml/min, to get rid of the air in the silica tube, open the temperature regulator of electric furnace behind 15～20min, and be warming up to 800 ℃, with stainless steel substrates thermal treatment 20～30min under this temperature, close argon gas then, and resistance furnace is cooled to room temperature;
(7) preparation of carbon nano tube compound material in the tube type resistance furnace
1. cleaned silica tube is put into tube type resistance furnace, here silica tube is the reaction chamber of preparation carbon nano tube compound material; Stainless steel substrates is placed quartz boat, and stainless steel substrates here promptly is required catalyzer and the carrier of preparation carbon nano tube compound material; The quartz boat that stainless steel substrates is housed is put into the middle part of silica tube, i.e. the high temperature of tube type resistance furnace and constant temperature section, with the stopper shutoff of two ends, the silica tube left and right sides, the left end mouth of pipe is connected into hydrogen pipe and tunger tube, the right-hand member mouth of pipe escape pipe of ining succession;
2. on hydrogen pipeline, connect the Erlenmeyer flask that dimethyl sulphide is housed, colourless liquid dimethyl sulphide 50～100ml is joined in the water white Erlenmeyer flask, and with between the T-valve on this Erlenmeyer flask access hydrogen pipe, the T-valve on the left side is connected with hydrogen flowing quantity and takes into account hydrogen gas cylinder, and the T-valve on the right connects the hydrogen pipe and is connected in the silica tube; Dimethyl sulphide liquid can be brought in the silica tube by hydrogen, by controlling the flow of two T-valve and change hydrogen, can regulate the input period and the flow of dimethyl sulphide;
3. open the argon gas valve, regulate argon flow amount control and count to 200ml/min, import argon gas with this flow in silica tube, the time of input is 15～20min, drives away the air in the silica tube, and is discharged by escape pipe; Open hydrogen gas cylinder, and regulate two T-valve, regulate hydrogen flowing quantity control meter, in silica tube, import hydrogen with this flow to 100～200ml/min;
4. open the temperature regulator of tube type resistance furnace, make it be warming up to 950～1200 ℃;
5. regulate argon flow amount control meter to 800～1800ml/min; Regulate two T-valve, dimethyl sulphide in the Erlenmeyer flask generation steam that evaporates, be brought in the silica tube by hydrogen, the time of input is 15～30min, be that dimethyl sulphide at 950～1200 ℃ scission reaction takes place down, decompose in being placed with the quartz boat of stainless steel substrates, grow, generate carbon nano tube compound material, the scission reaction chemical equation that dimethyl sulphide takes place is as follows:
In the formula: C: carbon
H
2S: hydrogen sulfide
CH
4: methane
SS:stainless steel stainless steel substrates
6. after the scission reaction of dimethyl sulphide is carried out fully, close the temperature regulator of tube type resistance furnace, close hydrogen flowing quantity control meter, T-valve simultaneously; And continuing to feed argon gas, the product in the silica tube cools to room temperature with the furnace, closes argon flow amount control meter after cooling is good, opens silica tube, takes out quartz boat;
7. collect the black solid powder in the quartz boat, this black solid powder is the carbon nano tube compound material that iron sulphide is filled.
Pressed powder to the black for preparing is analysis and the relevant characterization that carbon nano tube compound material carries out pattern, composition, purity, performance; With field emission scanning electron microscope product is carried out morphology analysis; With high resolution transmission electron microscopy microstructure of product is analyzed; With X ray energy dispersion instrument the composition of product is analyzed; With vector network analyzer its microwave absorbing property is tested and analyzed.
Conclusion: the product surface is a black, the partially filled carbon nano tube compound material that iron sulphide is arranged; Its diameter is 70～100nm, and length can reach tens microns; And comprise sulphur, iron, carbon in the product; Reflection loss in low frequency section maximum can reach 29.58dB, promptly has good microwave absorbing property.
In the preparation concrete steps of the carbon nano tube compound material that above-mentioned iron sulphide is filled; the preparation of carbon nano tube compound material is carried out in tube type resistance furnace; silica tube is a reaction chamber; temperature rises to 950～1200 ℃ and under this temperature; keep reaction 15～30min; this period is gas phase generation, deposition, modality, product growth period, stops the heating back and be cooled to room temperature under argon shield.
In the preparation concrete steps of the carbon nano tube compound material that above-mentioned iron sulphide is filled, the flow range of used hydrogen is 100～200ml/min.
The carbon nano tube compound material that iron sulphide of the present invention is filled uses as electromagnetic wave absorbent material and electromagnetic shielding material.
Use the method for the carbon nano tube compound material of iron sulphide filling of the present invention to be: carbon nano tube compound material of the present invention to be dispersed in paraffin or the Resins, epoxy, to be coated in required body surface then.
The present invention has following characteristics:
(1) carbon nano tube compound material of iron sulphide filling of the present invention has good absorption of electromagnetic wave performance, can make electromagnetic shielding and microwave absorbing material and use.
(2) carbon nano tube compound material of iron sulphide filling is carbon source with the dimethyl sulphide, is the preparation of catalyzer direct in-situ with the stainless steel substrates, has simple, the characteristics such as the product feature is controlled, output height of reaction process flow process.
(3) can be by size, the growth time of control substrate stainless steel substrates, and carbon source concentration and the isoparametric adjusting of gas ratio reach the control to carbon nanotube output, so the present invention has characteristics such as technology is easy, controllability good, can produce in batches.
Description of drawings
Fig. 1 is an employed device synoptic diagram in concrete the enforcement.Wherein, 1 expression silica tube; 2 expression high-temperature tubular resistance furnaces; 3 expression quartz boats; 4 expression furnace temperature controllers; 5 expression argon gas gas storage steel cylinders; 6 expression hydrogen gas storage steel cylinders; The Erlenmeyer flask of dimethyl sulphide liquid is equipped with in 7 expressions; 8 expression vent gas treatment bottles; 9 express tracheae.
Fig. 2 is the stereoscan photograph that adopts the prepared carbon nano tube compound material of the present invention.From figure as can be seen, prepared carbon nano tube compound material diameter is even, is about 70-100nm, and length can reach several microns, and nanotube product tube wall is smooth, the purity height.
Fig. 3 is the transmission electron microscope photo that adopts the carbon nano tube compound material of the present invention's preparation.Filled other material as can be seen from Figure in the carbon nanotube.
Fig. 4 is the high-resolution-ration transmission electric-lens photo that adopts the carbon nano tube compound material of the present invention's preparation.The spacing of product cladding material is 0.34nm as can be seen from Figure, corresponding to (002) face of graphite, the outer carbon nanotube that is is described; The spacing of material inside is respectively 0.19nm and 0.24nm, corresponding to the Fe of hexagonal structure
7S
8(235) and (115) crystal face.The presentation of results product is to be filled with Fe in the inner chamber
7S
8Material, the product that promptly obtains are the carbon nano tube compound material that iron sulphide is filled.
Fig. 5 is X ray energy dispersion (EDS) spectrogram that adopts the carbon nano tube compound material of the present invention's preparation.Comprise sulphur, iron, carbon from figure in the provable material, the Cu peak information among the figure comes from employed copper mesh when analyzing.
Fig. 6 adopts the carbon nano tube compound material of the present invention's preparation to be scattered in the paraffin at the microwave reflection attenuation test of microwave frequency band figure as a result.Figure floating coat thickness is 2mm, and maximum reflection loss reaches 29.58dB when 14.80GHz
Embodiment
The invention provides a kind of carbon nano tube compound material of iron sulphide filling of novelty, its preparation method also is provided, its reaction unit can be an experimental installation shown in Figure 1, also can design voluntarily.The structure of reaction unit is among Fig. 1: be the silica tube 1 of scalable turnover in high-temperature tubular resistance furnace 2, and in the central authorities of silica tube is that quartz boat 3 has been placed in the high temperature constant temperature district of high-temperature tubular resistance furnace, central part at silica tube is the constant temperature section, the stopper shutoff of its two-port, be provided with the inlet pipe of argon gas, hydrogen in its left port, be connected with the gas storage steel cylinder 5 of argon gas, gas storage steel cylinder 6 with hydrogen, the Erlenmeyer flask 7 of while hydrogen by dimethyl sulphide liquid is housed, the dimethyl sulphide volatilization carries it in the silica tube by hydrogen; Right-hand member at silica tube is connected with the liquid bottles 8 that can absorb tail gas, and is connected with escape pipe 9.It promptly is formed carbon nano tube compound material that reaction finishes back product on the stainless steel substrates in quartz boat 3.Below in conjunction with the drawings and specific embodiments the present invention is given further instruction.
Embodiment 1:
Device is as accompanying drawing 1.Silica tube, quartz boat, stainless steel substrates will clean, and keep clean, prevent because of pollution has side effects, and concrete preparation technology is as follows:
(1) the commercial stainless steel substrates of buying is cut into any size, in hydrochloric acid, soaks 10min and remove surface impurity, and then clean stand-by with ethanol.
(2) stainless steel substrates of above-mentioned processing is put into quartz boat, put into together in the silica tube reaction chamber again.
(3) with feeding the about 20min of argon gas (flow is 200ml/min) in the described silica tube reaction chamber of step (2) earlier, process furnace is warming up to 1000 ℃ then to get rid of the air in the reaction tubes.
(4) the argon flow amount 1700ml/min in the set-up procedure (3), and feed hydrogen and its flow is adjusted into 200ml/min, bring the carbon source dimethyl sulphide into reaction chamber reaction 15min by hydrogen simultaneously, reaction finishes, and stops hydrogen supply, and argon flow amount is reduced to 200ml/min, make silica tube under argon gas atmosphere, be cooled to room temperature, stop the argon gas supply, on stainless steel substrates, form black deposit, be carbon nano tube compound material.
Embodiment 2:
Preceding step is identical with step 1～3 in the specific embodiment 1, argon flow amount in the set-up procedure (4) is 1100ml/min then, and feed hydrogen and its flow is adjusted into 200ml/min, bring the carbon source dimethyl sulphide into reaction chamber reaction 30 minutes by hydrogen simultaneously, on stainless steel substrates, can form carbon nano tube compound material after reaction finishes.
Argon flow amount, argon flow amount in concrete the enforcement, temperature of reaction and reaction times length can change in certain limit, such as argon flow amount between 800～1800ml/min, hydrogen flowing quantity is between 100～300ml/min, temperature of reaction is between 950～1200 ℃, and reaction times 15～45min can both obtain carbon nano tube compound material.
Embodiment 3
Carbon nano tube compound material prepared among the embodiment 1 is dispersed in paraffin or the Resins, epoxy according to weight ratio at 1: 5, can be used as microwave absorbing material.When carbon nano tube compound material/when paraffin coating thickness is 2mm, maximum reflection loss reaches 29.58dB when 14.80GHz among the embodiment.
Claims (9)
1. the carbon nano tube compound material that iron sulphide is filled is characterized in that having iron sulphide in the inner chamber of carbon nanotube, and the molecular formula of wherein said iron sulphide is Fe
7S
8
2. the preparation method of the carbon nano tube compound material that iron sulphide according to claim 1 is filled is characterized in that the Fe in the carbon nanotube cavity
7S
8Original position is filled in the carbon nano tube growth process.
3. the preparation method of the carbon nano tube compound material that iron sulphide according to claim 2 is filled is characterized in that the preparation of the carbon nano tube compound material that iron sulphide is filled may further comprise the steps:
(1) stainless steel substrates is cut into any size, cleans stand-by.
(2) above-mentioned stainless steel substrates is put into process furnace; Feed the air in argon gas or the nitrogen eliminating reaction chamber earlier, then process furnace is warming up to temperature of reaction, temperature of reaction is between 950～1200 ℃.
(3) dimethyl sulphide steam is fed reaction chamber and react, stop the dimethyl sulphide steam supply after reaction finishes, make process furnace be cooled to room temperature, the black deposit that forms on stainless steel substrates is carbon nano tube compound material.
4. the preparation method of the carbon nano tube compound material that iron sulphide according to claim 3 is filled is characterized in that with the stainless steel substrates being catalyzer and substrate, is carbon source with the dimethyl sulphide, feed hydrogen and argon gas, at high temperature carries out prepared in reaction.
5. the preparation method of the carbon nano tube compound material that iron sulphide according to claim 4 is filled is characterized in that the preparation concrete steps of the carbon nano tube compound material that iron sulphide is filled are as follows:
(1) selected raw chemical material
Preparation carbon nano tube compound material required raw chemical material is carried out selected, and carries out the control of purity and precision:
Dimethyl sulphide: colourless liquid, purity 〉=99.0%;
Stainless steel substrates: adopt 304 stainless steel substrates, thickness≤0.2mm;
Dehydrated alcohol: colourless liquid, purity 〉=99.7%;
Deionized water: colourless liquid, purity 〉=99.7%;
Hydrochloric acid: colourless liquid, concentration 10.0～35.0%;
Argon gas: gas, purity 〉=99.9%;
Hydrogen: gas, purity 〉=99.99%;
(2) clean silica tube
With the inner and outer wall of tap water lavation, flushing silica tube, scrub the inwall of silica tube then with 500～1000ml deionized water, make its cleaning, clean two-port with dehydrated alcohol again, cleaning finishes to be placed on the platform dries, standby;
(3) clean quartz boat
Quartz boat is placed beaker, add deionized water 80～100ml, soak and jog beaker 4～6s, outwell deionized water; Add dehydrated alcohol 80～100ml then, be placed in the ultrasonic cleaner, ultrasonic cleaning 10～20min;
(4) drying treatment quartz boat
Place loft drier dry the taking-up of quartz boat after the ultrasonic cleaning, drying temperature is 100～150 ℃, and be 15～20min time of drying, takes out cooling, and is standby;
(5) clean stainless steel substrates
Stainless steel substrates is cut into suitable size (such as 1cm * 3cm), place beaker, to add hydrochloric acid 15～20ml, soaks 5～10min; Take out stainless steel substrates then and put into the beaker that fills 80～100ml dehydrated alcohol again, be placed in the ultrasonic cleaner, ultrasonic cleaning 10～20min, taking-up is dried, and is standby;
(6) handle stainless steel substrates
1. above-mentioned cleaned standby stainless steel substrates is placed quartz boat;
2. this quartz boat is put into the silica tube central section;
3. with the port shutoff of the silica tube left and right sides, left part connects argon gas and hydrogen pipe, and right part connects escape pipe;
4. open argon gas steel gas cylinder, flow is 100～200ml/min, to get rid of the air in the silica tube, open the temperature regulator of electric furnace behind 15～20min, and be warming up to 800 ℃, with stainless steel substrates thermal treatment 20～30min under this temperature, close argon gas then, and resistance furnace is cooled to room temperature;
(7) preparation of carbon nano tube compound material in the tube type resistance furnace
1. cleaned silica tube is put into tube type resistance furnace, stainless steel substrates is placed quartz boat, the quartz boat that stainless steel substrates is housed is put into the middle part of silica tube, be the high temperature and the constant temperature section of tube type resistance furnace, with the stopper shutoff of two ends, the silica tube left and right sides, the left end mouth of pipe is connected into hydrogen pipe and tunger tube, the right-hand member mouth of pipe escape pipe of ining succession;
2. on hydrogen pipeline, connect the Erlenmeyer flask that dimethyl sulphide is housed, colourless liquid dimethyl sulphide 50～100ml is joined in the water white Erlenmeyer flask, and with between the T-valve on this Erlenmeyer flask access hydrogen pipe, the T-valve on the left side is connected with hydrogen flowing quantity and takes into account hydrogen gas cylinder, and the T-valve on the right connects the hydrogen pipe and is connected in the silica tube.Dimethyl sulphide liquid can be brought in the silica tube by hydrogen, by controlling the flow of two T-valve and change hydrogen, can regulate the input period and the flow of dimethyl sulphide;
3. open the argon gas valve, regulate argon flow amount control and count to 200ml/min, import argon gas with this flow in silica tube, the time of input is 15～20min, drives away the air in the silica tube, and is discharged by escape pipe; Open hydrogen gas cylinder, and regulate two T-valve, regulate hydrogen flowing quantity control meter, in silica tube, import hydrogen with this flow to 100～200ml/min;
4. open the temperature regulator of tube type resistance furnace, make it be warming up to 950～1200 ℃;
5. regulate argon flow amount control meter to 800～1800ml/min; Regulate two T-valve, dimethyl sulphide in the Erlenmeyer flask generation steam that evaporates, be brought in the silica tube by hydrogen, the time of input is 15～30min, be that dimethyl sulphide at 950～1200 ℃ scission reaction takes place down, decompose in being placed with the quartz boat of stainless steel substrates, grow, generate carbon nano tube compound material, the scission reaction chemical equation that dimethyl sulphide takes place is as follows:
In the formula: C: carbon
H
2S: hydrogen sulfide
CH
4: methane
SS:stainless steel stainless steel substrates
6. after the scission reaction of dimethyl sulphide is carried out fully, close the temperature regulator of tube type resistance furnace, close hydrogen flowing quantity control meter, T-valve simultaneously; And continuing to feed argon gas, the product in the silica tube cools to room temperature with the furnace, closes argon flow amount control meter after cooling is good, opens silica tube, takes out quartz boat;
7. collect the black solid powder in the quartz boat, this black solid powder is the carbon nano tube compound material that iron sulphide is filled.
6. the preparation method of the carbon nano tube compound material that iron sulphide according to claim 5 is filled; it is characterized in that: the preparation of carbon nano tube compound material is carried out in tube type resistance furnace; silica tube is a reaction chamber; temperature rises to 950～1200 ℃ and under this temperature; keep reaction 15～30min; this period is gas phase generation, deposition, modality, product growth period, stops the heating back and be cooled to room temperature under argon shield.
7. the preparation method of the carbon nano tube compound material that iron sulphide according to claim 5 is filled, it is characterized in that: the flow range of used hydrogen is 100～200ml/min.
8. the application of the carbon nano tube compound material that iron sulphide according to claim 1 is filled is characterized in that the carbon nano tube compound material that described iron sulphide is filled uses as electromagnetic wave absorbent material and electromagnetic shielding material.
9. the application of the carbon nano tube compound material that iron sulphide according to claim 8 is filled, it is characterized in that using the method for the carbon nano tube compound material that described iron sulphide fills to be: the carbon nano tube compound material that iron sulphide is filled is dispersed in paraffin or the Resins, epoxy, is coated in required body surface then.
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