CN101047086A - Nano carbon pipe composite field-emission source and manufacturing method thereof - Google Patents
Nano carbon pipe composite field-emission source and manufacturing method thereof Download PDFInfo
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title abstract 4
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 93
- 239000000835 fiber Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 238000002360 preparation method Methods 0.000 claims abstract description 59
- 239000004744 fabric Substances 0.000 claims abstract description 50
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 47
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 560
- 239000002041 carbon nanotube Substances 0.000 claims description 517
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 517
- 239000000725 suspension Substances 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 34
- 239000004917 carbon fiber Substances 0.000 claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- 238000001962 electrophoresis Methods 0.000 claims description 29
- 239000012535 impurity Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 238000005119 centrifugation Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000010935 stainless steel Substances 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 15
- 238000010008 shearing Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 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 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
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- 239000000047 product Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 5
- 208000006735 Periostitis Diseases 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 210000003460 periosteum Anatomy 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000009940 knitting Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 description 1
- MIINHRNQLVVCEW-UHFFFAOYSA-N 132-16-1 Chemical compound [Fe+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MIINHRNQLVVCEW-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The present invention relates to a nano carbon tube composite field emission source. It includes nano carbon tube membrane which is grown on the substrate and can be used as electronic field emission source. The described substrate is of conductive fibre braided rope or braided fabric, its fibre diameter range is 1-20 microns. The preparation method of said composite field emission source includes the following steps: under the condition of normal temperature and normal pressure utilizing phonochemical method to prepare nano carbon tube; adopting the processes of centrifugal separation, filtration, surface active ultrasonic dispersion, chemical corrosion, selective oxidation and ultrasonic etching, etc. to purify and shear nano carbon tube; then utilizing electrophoretic deposition process to make the purified and sheared nano carbon tube be firmly deposited on the conductive fibre braided rope or braided fabric so as to form the invented nano carbon tube composite field emission source.
Description
Technical field
The present invention relates to compound field emission source of a kind of CNT (carbon nano-tube) and preparation method thereof, particularly relate to the phonochemistry method and under normal temperature and condition of normal pressure, prepare CNT (carbon nano-tube), and utilize electrophoretic deposition that prepared CNT (carbon nano-tube) is deposited on carbon fiber or metal (or alloy) fibrous braid (cloth or the rope) substrate, make the method for the compound field emission source of CNT (carbon nano-tube).
Background technology
Because CNT (carbon nano-tube) has excellent electric conductivity, high mechanical strength and chemical stability, and very high form factor (ratio of length and radius), make it become desirable electron field emission materials, thereby in the development of field emission illumination lamp of new generation, Field Emission Display (FED) and other microelectronics vacuum device, occupy illustrious status.
(comprising Thermal CVD and all kinds of plasma enhanced chemical vapor deposition-PECVD), is three kinds of common methods of preparation individual layer CNT (carbon nano-tube) and multi-layer nano carbon pipe for arc process, laser method and chemical vapor deposition (CVD) method.Owing to can control effectively to chemical vapor deposition processes, people utilize the chemical vapour deposition technique can not only prepared in batches high-purity individual layer CNT (carbon nano-tube) and multi-layer nano carbon pipe, and can prepare with arc process and laser method and be difficult to the orientation MWNTs film that maybe can't synthesize.Prepare CNT (carbon nano-tube) with above-mentioned three kinds of methods, all need high temperature, vacuum or other special process condition.
As everyone knows, utilize ultrasonic sound cavitation effect can effectively carry out chemical breakdown and synthetic.Recently use the phonochemistry method, under normal temperature and condition of normal pressure, successfully synthesize individual layer CNT (carbon nano-tube) [1] (J.Am.Chem.Soc.126 (2004) 15982. for [1] S.-H.Jeong, et al.).Method with the synthetic individual layer CNT (carbon nano-tube) of phonochemistry method is as follows: at first prepare the solution of ferrocene in paraxylene with certain molar concentration, and add the SiO of some in the solution that has prepared
2Powder; With 200W titanium probe supersonic source solution is carried out sonicated then, can obtain the individual layer CNT (carbon nano-tube) and (contain SiO in the product
2Particle, catalyst nano particle and impurity such as a small amount of amorphous carbon particle and graphite scrap).According to the phonochemistry principle, sound cavitation effect can cause the decomposition of ferrocene and paraxylene.The iron atom that is decomposed out by ferrocene is at SiO
2Particle surface is assembled and the formation iron nano-particle; In localized regions of elevated temperature in the acoustic cavitation bubble and the hyperbaric environment and under the catalytic action of iron nano-particle, the carbon atom that decomposes out from ferrocene and paraxylene forms individual layer CNT (carbon nano-tube) and impurity such as a spot of amorphous carbon particle and graphite scrap.Experiment shows that (1) is SiO in phonochemistry is synthetic
2Particle plays an important role, and does not add SiO
2Powder just can not form the individual layer CNT (carbon nano-tube); (2) ferrocene content has significant impact to product, and content is low excessively to make the productive rate of individual layer CNT (carbon nano-tube) very little, and too high levels can produce too much amorphous carbon particle and graphite scrap, even multi-layer nano carbon pipe; An amount of ferrocene is to obtain key pure, high yield individual layer CNT (carbon nano-tube).The phonochemistry method not only can the high-purity individual layer CNT (carbon nano-tube) of large-scale production, and compares with arc process, laser method and CVD method, has that equipment and preparation technology are simple, energy savings and the advantage that reduces cost.
According to principles of electrostatics, the projection of body surface can cause the enhancing of local electric field, and field enhancement factor (β) is inversely proportional to the radius of curvature (r) of projection, is directly proportional with the height (h) of projection (β ∝ h/r).The surface irregularity of carbon fiber woven cloth, they itself are exactly a kind of good field emission source.With the chemical vapour deposition technique compound field emission source that multi-layer nano carbon pipe forms of on carbon fiber woven cloth, growing, show high field enhancement factor (β=1.88 * 10
4), than the high about order of magnitude [2] ([2] S.H.Jo, Z.F. Ren et al., Appl.Phys.Lett., 85 (2004) 810.) of β value of the nano-sized carbon periosteum of on smooth substrates such as Si or glass, growing.Nearest research [3] ([3] J.Y.Huang, Z.F.Ren et al., Appl.Phys.Lett., 87 (2005) 53110) shows that the excellent field emission performance of the compound field emission source of CNT (carbon nano-tube) is caused by the multistage effect of field emission.
With silk screen print method CNT (carbon nano-tube) paste (mixture of CNT (carbon nano-tube) and organic bond) is coated on the substrate, make the CNT (carbon nano-tube) field-transmitting cathode, it has been applied to the making [4] (Carbon 38 (2000) 169 for [4] Y.Saito, S.Uemura) of CNT (carbon nano-tube) light-emitting component.Screen printing technique technology is simple, is suitable for making the large tracts of land field-transmitting cathode; But have also that field transmitting uniformity is poor, resolution is low, the CNT (carbon nano-tube) utilance is low and needs such as could use after activating at shortcoming.As everyone knows, utilize electrophoretic deposition can be on the substrate of any complicated shape the cover layer [5] (Annu.Rev.Mater.Sci.29 (1999) 327 for [5] O.O.Van der Biest, et al.) of deposition and substrate strong bonded.In recent years, people have been applied to electrophoretic deposition the preparation [6] of CNT (carbon nano-tube) field-transmitting cathode (APL 78 (2001) 1547 for [6] O.Zhou, et al.; 84 (2004) 3738.).The step for preparing the CNT (carbon nano-tube) field-transmitting cathode with electrophoretic deposition is summarized as follows: at first the CNT (carbon nano-tube) of some is put into solution (organic solutions such as deionized water or ethanol), and formed steady suspension through sonicated; Then, in suspension, add " charged body " (MgCl
2Or electrolyte such as NaOH), makes CNT (carbon nano-tube) " adion " and electrically charged, for example " absorption Mg
2+" positively charged, or " absorption OH
-" and electronegative; Subsequently, insert two electrodes (one of them is a substrate, the entrained opposite polarity of the polarity of underlayer electrode and CNT (carbon nano-tube)) in suspension, CNT (carbon nano-tube) will and be deposited on the substrate to the migration of underlayer electrode direction behind the added electric field.Compare with silk screen print method, the CNT (carbon nano-tube) negative electrode of electrophoretic deposition preparation has that CNT (carbon nano-tube) is firm with substrate binding, field transmitting uniformity, good stability and resolution advantages of higher.In addition, also to have a CNT (carbon nano-tube) utilance height, productive rate high and be not subjected to characteristics such as substrate dimension restriction for electrophoretic deposition.
Summary of the invention
The objective of the invention is to launch multistage effect principle based on the field, utilize CNT (carbon nano-tube) that electrophoretic deposition will prepare with the phonochemistry method and purified and that shear, deposit on carbon fiber or metal (or alloy) fibrous braid (cloth or rope), formation has the compound field emission source of CNT (carbon nano-tube) (can reduce the operating voltage and the energy consumption of feds) of high field enhancement factor, and a kind of method for preparing the compound field emission source of this CNT (carbon nano-tube) is provided.
The invention provides the compound field emission source of a kind of CNT (carbon nano-tube), it is made up of substrate and the nano-sized carbon periosteum that deposits on substrate, it is characterized in that described substrate is the conductive fiber braid, described braid comprises kernmantle or woven cloth, and the fiber diameter range of this braid is 1～20 μ m.
In above-mentioned technical scheme, described fibrous braid can be fibrage rope or fibre knitting cloth, and used fiber comprises carbon fiber and iron, nickel, aluminium, copper and alloy fiber thereof, particularly Fe-Al-Cr alloy fiber and stainless steel fibre; Described fiber diameter range is 1～20 μ m.
A kind of method for preparing the compound field emission source of CNT (carbon nano-tube) provided by the invention may further comprise the steps:
(a) preparation of nano carbon pipe organic growth liquid: CNT (carbon nano-tube) organic growth liquid is made up of organic solvent, organic magnesium-yttrium-transition metal compound (as catalyst) and oxide particle (as carrier, providing the nucleation surface for CNT (carbon nano-tube) forms); The molar concentration of transiting group metal elements is 2 * 10 in the organic growth liquid
-4Mol/L～2 * 10
-2Mol/L, the addition of carrier particles is 10～100g/L;
(b) phonochemistry of CNT (carbon nano-tube) growth: under normal temperature and condition of normal pressure, above-mentioned organic growth liquid is carried out sonicated, and the product of the phonochemical reaction of organic growth liquid is CNT (carbon nano-tube), a spot of graphite scrap and amorphous carbon nano particle and catalyst metal particles etc.; Organic growth liquid after the sonicated is carried out centrifugation and filtration, thereby obtain containing the solid product of CNT (carbon nano-tube);
(c) suspension of preparation of nano carbon pipe: suspension is by water or organic solvent, form with phonochemistry method synthetic CNT (carbon nano-tube) and " charged body " (making CNT (carbon nano-tube) carry electric charge); Wherein the content range of CNT (carbon nano-tube) is 1～1000mg/L, and the concentration range of " charged body " is 0.01～1g/L in suspension;
(d) electrophoretic deposition of CNT (carbon nano-tube): in the container that fills CNT (carbon nano-tube) suspension, insert two electrodes, one of them electrode is the conductive fiber braid, the entrained opposite polarity of its polarity and CNT (carbon nano-tube), two distance between electrodes are 1～15cm, voltage is 1～1, and 000V, electrophoresis time are 0.5～10 minute, CNT (carbon nano-tube) deposits on the conductive fiber braid by electrophoresis process under External Electrical Field, forms the compound field emission source of CNT (carbon nano-tube).
In technique scheme, before the suspension of preparation of nano carbon pipe, can adopt the impurity in purifying and shearing step removal step (b) the gained solid product, obtain length controlled and relative homogeneous high purity CNT (carbon nano-tube), thereby help improving the field transmitting uniformity and the stability of compound field emission source.Except that CNT (carbon nano-tube), also contain impurity such as catalyst metal particles, oxide particle, graphite scrap and amorphous carbon nano particle in the solid product of phonochemical reaction.Utilize the difference of the antiacid corrosive power of metal and metal oxide and carbonaceous material, be easy to by strong acid erosion removal metal and metal oxide particle.Amorphous carbon nano particle and graphite scrap attached to the surface of CNT (carbon nano-tube), in order to remove these carbon-containing impurities, at first make carbon-containing impurities from the CNT (carbon nano-tube) sur-face peeling with the ultrasonic dispersion technology of surface activity usually; Utilize the fault of construction of carbon-containing impurities many then, the characteristics of chemism height and easier oxidation adopt selective oxidation technology (oxidation or rare (nitre) sour circumfluence method in 500 ℃ of following air) to remove carbon-containing impurities.The fault of construction of CNT (carbon nano-tube) has higher energy, and available ultrasonic etching method is sheared CNT (carbon nano-tube), the length and the uniformity thereof of control CNT (carbon nano-tube).
In technique scheme, described organic solvent is the main carbon source of CNT (carbon nano-tube) growth, should select nontoxic or toxicity is little, and can dissolve the organic solvent of selected organo-metallic compound (as catalyst), and they comprise dimethyl formamide (DMF) C
3H
7NO, paraxylene C
8H
10, naphthalane C
10H
18Or decane C
10H
22
In technique scheme, described organo-metallic compound provides required metallic catalyst for the CNT (carbon nano-tube) growth.Transiting group metal elements such as Fe, Ni, Co and Mo are CNT (carbon nano-tube) growth metallic catalysts commonly used; Organo-metallic compound comprises ferrocene C
10H
10Fe, iron pentacarbonyl Fe (CO)
5, nickel carbonyl Ni (CO)
4, phthalocyanine cobalt C
32H
16N
8Co (PcCo) or hexacarbonylmolybdenum Mo (CO)
6Deng.In CNT (carbon nano-tube) organic growth liquid, the molar concentration scope of above-mentioned transiting group metal elements is 2 * 10
-4Mol/L～2 * 10
-2Mol/L.
In technique scheme, when the organic growth liquid of preparation of nano carbon pipe, can also add surfactant, promote the nucleation and the growth of CNT (carbon nano-tube).Surface active element commonly used is nonmetalloid S, P and B, and described surfactant comprises thiophene C
4H
4S, sulfolane C
4H
8O
2S, triethyl phosphate (C
3H
5)
3O
4P, diphenylprop thiazolinyl borine (C
15H
15B) or triphenyl borine (C
18H
15B).Surfactant is selected and should be mated with the selection of organic solvent and organo-metallic compound, so that bring into play the effect of surfactant to greatest extent; The molar concentration of above-mentioned surface active element is 2 * 10 in the solution
-5Mol/L～2 * 10
-3Mol/L.
In technique scheme, described carrier granular provides the nucleation surface for the CNT (carbon nano-tube) growth, can select to have chemically inert oxide as carrier, comprises silica, aluminium oxide or magnesium oxide powder, and the diameter range of powder particle is 0.5～5mm.
In technique scheme, the operating frequency range of supersonic source is 15～32KHz in the CNT (carbon nano-tube) phonochemistry is synthetic, and power bracket is 100～2000W, and the time range of sonicated is 5～40 minutes.
In technique scheme, utilize chemical corrosion method can easily remove catalyst nano particle and oxide particle in the product, for example use hydrochloric acid (or sulfuric acid, or nitric acid) aluminium oxide or magnesium oxide and catalyst granules in the product can be removed, silica and catalyst granules can be removed with hydrofluoric acid.
In technique scheme, utilizing CNT (carbon nano-tube), different with the initial oxidation temperature of carbon-containing impurities (the former is about 580 ℃, the latter is about 480 ℃), the selective oxidation that can be used under 500 ℃ is removed carbon-containing impurities, also can utilize rare (nitre) sour circumfluence method to remove carbon-containing impurities, obtain pure CNT (carbon nano-tube).
In technique scheme, the CNT (carbon nano-tube) behind the purifying is put into nitric acid-sulfuric acid mixture liquid, CNT (carbon nano-tube) is effectively sheared the length and the uniformity thereof of control CNT (carbon nano-tube) by the sonochemistry etching.
In technique scheme, the solvent of CNT (carbon nano-tube) suspension is water H
2O, methyl alcohol CH
4O, ethanol C
2H
6O, isopropyl alcohol C
3H
8O or dimethyl formamide C
3H
7NO, the content range of CNT (carbon nano-tube) is 1-1000mg/L in the suspension.
In technique scheme,, need in suspension, to add MgCl for realizing the electrophoretic deposition of CNT (carbon nano-tube)
2, Mg (NO
3)
2, AlCl
3Or NaOH etc. " charged body ", make the CNT (carbon nano-tube) in the suspension electrically charged: for example, to add MgCl
2Make CNT (carbon nano-tube) " absorption Mg
2+" and positively charged, add NaOH and make CNT (carbon nano-tube) " absorption OH
-" and electronegative." charged body " concentration range in solution is 0.01-1g/L.
In technique scheme, when the conductive fiber braid is carbon, aluminium or copper fibrous braid, need carbide former Fe, Ti, Zr, V, Nb, Mo or the W film of the about 10-100nm of deposit thickness on fibrous braid, in order to strengthen the bonding force of CNT (carbon nano-tube) and fibrous braid.
The present invention adopts the phonochemistry method to prepare CNT (carbon nano-tube) under normal temperature and condition of normal pressure, adopt methods such as chemical corrosion, the ultrasonic dispersion of surface activity and selective oxidation to carry out Purification of Carbon Nanotubes, adopt ultrasonic etching method that the purification of nanocarbon pipe is sheared, and by electrophoretic deposition with purifying and the CNT (carbon nano-tube) after shearing be deposited on securely on carbon fiber or metal (or alloy) fibrous braid (cloth or rope), make the compound field emission source of CNT (carbon nano-tube).
Compared with the prior art, the present invention has the following advantages:
(1) compares the equipment of CNT (carbon nano-tube) phonochemistry synthetic method and technology is more simple, efficient is higher, energy consumption and cost are lower, be more suitable for large-scale production with laser method, arc process and chemical vapour deposition technique.
(2) compare with silk screen print method, the CNT (carbon nano-tube) utilance of electrophoretic deposition is higher, and favourable son reduces cost; Nano-sized carbon periosteum and substrate with the electrophoretic deposition preparation have stronger cementability, and the field transmitting uniformity and the stability of prepared CNT (carbon nano-tube) negative electrode all are better than silk screen print method.
(3) with electrophoresis CNT (carbon nano-tube) is deposited on the compound field emission source of making on the fibrous braid, has high field enhancement factor, can reduce the operating voltage and the energy consumption of feds.
Description of drawings
Fig. 1: the present invention prepares the schematic diagram of CNT (carbon nano-tube) with the phonochemistry method
Fig. 2: the present invention prepares the schematic diagram of plane CNT (carbon nano-tube) field emission source with electrophoretic deposition
Fig. 3: the present invention prepares the schematic diagram of linear nano carbon tube field emission source with electrophoretic deposition
Wherein, the 101st, the titanium ultrasonic probe; The 102nd, CNT (carbon nano-tube) organic growth liquid; The 103rd, carrier granular; The 104th, catalyst granules; The 201st, DC power supply; The 202nd, CNT (carbon nano-tube) suspension; The 203rd, the metal plate electrode; The 204th, the planar substrate electrode; The 205th, direction of an electric field; The 301st, linear underlayer electrode; The 302nd, the cylinder type metal electrode; The 303rd, CNT (carbon nano-tube) suspension; The 304th, DC power supply.
Embodiment
Below in conjunction with drawings and Examples the present invention is provided and to further describe:
Embodiment 1:
Present embodiment adopts the Fe-Al-Cr fibre knitting cloth as substrate, and Fe-Al-Cr woven cloth area is 2 * 2cm
2, the Fe-Al-Cr fibre diameter is 1 μ m.The step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure 50mL paraxylene C
8H
10, add the silicon oxide powder that 20mg ferrocene and 2 gram average particulate diameters are about 2mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid 102 is put into ice bath, inserting ultrasonic probe 101 then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 300W, and the sonicated time is 20 minutes; Phonochemical reaction takes place in organic growth liquid 102 in the sonicated process, generates CNT (carbon nano-tube) on silica support 103 surfaces, generates the impurity that comprises catalyst granules 104 and amorphous carbon and graphite nanoparticles simultaneously, makes the color blackening gradually of organic solution; After treating that sonicated finishes, organic solution is carried out centrifugation and the big impurity particle of filtration treatment removal, obtain containing the solid product of CNT (carbon nano-tube) and small impurities particle.
(3) preparation of nano carbon pipe alcohol suspension: measure 100mL ethanol, add 1mg step (2) synthetic solid product that contains CNT (carbon nano-tube) and 5mg MgCl
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(4) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension 202 for preparing, insert two electrodes, electrode links to each other with negative pole with the positive pole of DC power supply 201 respectively by lead; In example shown in Figure 2, negative pole is a Fe-Al-Cr fibre knitting cloth 204, and just very the spacing of 203, two electrodes of gold plaque is 2cm, and voltage is 100V, and electrophoresis time is 3 minutes.Under above-mentioned electrophoretic deposition condition, positively charged CNT (carbon nano-tube) will move against direction of an electric field 205, and be deposited on the Fe-Al-Cr fibre knitting cloth, obtain the compound field emission source of plane CNT (carbon nano-tube).
Embodiment 2:
Present embodiment adopts carbon fiber woven cloth as substrate, and the area of carbon fiber woven cloth is 2 * 2cm
2, the carbon fiber diameter is 2 μ m.The step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron-beam evaporation Ti film: deposited by electron beam evaporation method evaporation on above-mentioned carbon fiber woven cloth is thick to be the Ti film of 20nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and carbon fiber substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: measure the silicon oxide powder that 50mL decane, adding 2mg iron pentacarbonyl and 0.5g average particulate diameter are about 3mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 2000W, and the sonicated time is 5 minutes; Organic growth liquid generation phonochemical reaction in the sonicated process generates CNT (carbon nano-tube) and carbon-containing impurities particle and catalyst granules, makes the color blackening gradually of organic solution; After treating that sonicated finishes, organic solution is carried out centrifugation and the big impurity particle of filtration treatment removal, obtain containing the solid product of CNT (carbon nano-tube) and other little impurity particle.
(4) preparation of nano carbon pipe water slurry: measure the 100mL deionized water, add 2.5mg step (3) synthetic CNT (carbon nano-tube) and 0.5mgMgCl
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition: (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the carbon fiber woven cloth of above-mentioned plating Ti, gold plaque just very, the spacing of two electrodes is 0.5cm, and voltage is 30V, and electrophoresis time is 0.5 minute.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) will be deposited on the carbon fiber woven cloth of plating Ti securely, obtain the compound field emission source of plane CNT (carbon nano-tube).
Embodiment 3:
Preparation process adopts carbon fiber woven cloth as substrate with embodiment 2, and the area of carbon fiber woven cloth is 2 * 2cm
2, the carbon fiber diameter is 3 μ m.The step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron beam evaporation Mo film: deposited by electron beam evaporation method evaporation on above-mentioned carbon fiber woven cloth is thick to be the Mo film of 5nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and carbon fiber substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: the silicon oxide powder and the 0.1mg thiophene that measure the 50mL naphthalane, add the 4mg nickel carbonyl, the 0.5g average particulate diameter are about 1mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 1500W, and the sonicated time is 5 minutes; Organic growth liquid generation phonochemical reaction in the sonicated process generates CNT (carbon nano-tube) and carbon-containing impurities particle and catalyst granules, makes the color blackening gradually of organic solution; Owing to add the surfactant thiophene, phonochemical reaction is quickened, product increases; After treating that sonicated finishes, organic solution is carried out centrifugation and the big impurity particle of filtration treatment removal, obtain containing the solid product of CNT (carbon nano-tube) and other little impurity particle.
(4) preparation of nano carbon pipe water slurry: measure the 100mL deionized water, add 1mg step (3) synthetic solid product that contains CNT (carbon nano-tube) and 2.5mgNaOH; Therefore, CNT (carbon nano-tube) is electronegative in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the present embodiment, because CNT (carbon nano-tube) is electronegative, the polarity of planar substrate electrode just should be (its polarity should be opposite with a CNT (carbon nano-tube) electrically charged polarity), therefore electrode links to each other the positive pole of DC power supply with substrate (carbon fiber woven cloth of plating Mo), and negative pole links to each other with golden plate electrode; The spacing of two electrodes is 5cm, and voltage is 100V, and electrophoresis time is 2 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) will be deposited on the carbon fiber woven cloth of above-mentioned plating Mo securely, obtain the compound field emission source of plane CNT (carbon nano-tube).
Embodiment 4:
Present embodiment adopts the carbon fiber knit rope as substrate, and the length of carbon fiber knit rope is 10cm, and the carbon fiber diameter is 4 μ m.The step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron beam evaporation Fe film: deposited by electron beam evaporation method evaporation on above-mentioned carbon fiber knit rope is thick to be the Fe film of 40nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and carbon fiber substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: the 1.5g alumina powder and the 0.3mg sulfolane that measure the 50mL dimethyl formamide, add 28.5mg phthalocyanine cobalt, average particulate diameter are about 4mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 16kHz, ultrasonic power are 600W, and the sonicated time is 10 minutes; Organic growth liquid generation phonochemical reaction in the sonicated process generates CNT (carbon nano-tube) and carbon-containing impurities particle and catalyst granules, makes the color blackening gradually of organic solution; Owing to add the surfactant sulfolane, phonochemical reaction is quickened, product increases; After treating that sonicated finishes, organic solution is carried out centrifugation and the big impurity particle of filtration treatment removal, obtain containing the solid product of CNT (carbon nano-tube) and other little impurity particle.
(4) Purification of Carbon Nanotubes and shearing: in the solid product that after centrifugation and filtration treatment, obtains, except that containing CNT (carbon nano-tube), also have other impurity.Before formulated suspension is carried out electrophoretic deposition, above-mentioned solid product is carried out purifying: utilize ultrasonic dispersion that CNT (carbon nano-tube) is separated with carbon-containing impurities (amorphous carbon nano particle and graphite scrap), use dissolving with hydrochloric acid aluminium oxide and catalyst granules then, and, obtain high-purity nm carbon pipe with nitric acid circumfluence method and air oxidation process removing carbon-containing impurities; And adopt ultrasonic etching method that gained high-purity nm carbon pipe is sheared.
(5) preparation of nano carbon pipe alcohol suspension: measure 100mL ethanol, add high-purity nm carbon pipe and the 20mg AlCl of 50mg with step (3) and (4) preparation
3Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(6) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 3): in the CNT (carbon nano-tube) suspension 303 for preparing, insert two electrodes, wherein positive pole is that radius is metal (gold) cylinder 302 of 2cm, place the axial location of cylinder type positive pole as the carbon fiber knit rope 301 of the above-mentioned plating Fe of negative pole, adjusting voltage across poles by DC power supply 304 is 100V, and electrophoresis time is 2 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) will be deposited on the carbon fiber knit rope of above-mentioned plating Fe securely by electrophoresis process, obtain the compound field emission source of linear nano carbon tube.Because deposition is CNT (carbon nano-tube) purified and that shear, the performance of the compound field emission source of present embodiment preparation is improved greatly.
Embodiment 5
Present embodiment adopts the stainless steel fibre woven cloth as substrate, and the area of stainless steel fibre woven cloth is 2 * 2cm
2, fibre diameter is 5 μ m, the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL paraxylene, adding 39.6mg hexacarbonylmolybdenum, 2g average particulate diameter are about alumina powder and the 1.1mg triethyl phosphate of 5mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 30kHz, ultrasonic power are 500W, and the sonicated time is 10 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(3) all the step 4 with embodiment 4 is identical with condition with shearing step for Purification of Carbon Nanotubes.
(4) preparation of nano carbon pipe isopropanol suspension: measure the 100mL isopropyl alcohol, add high-purity nm carbon pipe and the 50mgAlCl of 20mg with step (2) and (3) preparation
3Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the stainless steel fibre woven cloth, gold plaque just very, and the spacing of two electrodes is 10cm, and voltage is 500V, and electrophoresis time is 4 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) will be deposited on the stainless steel fibre woven cloth, obtain the compound field emission source of plane CNT (carbon nano-tube) of function admirable.
Embodiment 6
Present embodiment adopts the stainless steel fibre kernmantle as substrate, and the length of fibrage rope is 8cm, and fibre diameter is 10 μ m, and the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL naphthalane, adding 171mg nickel carbonyl, 2.5g average particulate diameter are about alumina powder and the 1.3mg thiophene of 4mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 100W, and the sonicated time is 40 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(3) Purification of Carbon Nanotubes is all identical with embodiment 4 with condition with the shearing step.
(4) preparation of nano carbon pipe dimethyl formamide suspension: measure the 100mL dimethyl formamide, add high-purity nm carbon pipe and the 15mg MgCl of 0.04mg with step (2) and (3) preparation
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 3): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein positive pole is that radius is metal (gold) cylinder of 2cm, stainless steel fibre kernmantle negative pole is positioned at the axial location of cylinder type positive pole, voltage across poles is 150V, and electrophoresis time is 1 minute.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the stainless steel fibre kernmantle by electrophoresis process, obtains the compound field emission source of linear nano carbon tube of function admirable.
Embodiment 7:
Present embodiment adopts carbon fiber woven cloth as substrate, and the area of carbon fiber woven cloth is 2 * 2cm
2, fibre diameter is 15 μ m, the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron beam evaporation V film: deposited by electron beam evaporation method evaporation on above-mentioned carbon fiber knit rope is thick to be the V film of 1nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and carbon fiber substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL dimethyl formamide, adding 46.5mg ferrocene, 3g average particulate diameter are about magnesium oxide powder and the 8.5mg triphenyl borine of 0.5mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 400W, and the sonicated time is 20 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(4) all the step 4 with embodiment 4 is identical with condition with shearing step for Purification of Carbon Nanotubes.
(5) preparation of nano carbon pipe methanol suspension: measure 100mL methyl alcohol, add high-purity nm carbon pipe and the 3.5mgAlCl of 2mg with step (3) and (4) preparation
3Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(6) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the carbon fiber woven cloth of plating V, stainless steel substrates just very, the spacing of two electrodes is 1cm, and voltage is 40V, and electrophoresis time is 5 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the carbon fiber woven cloth of plating V securely by electrophoresis process, obtains the compound field emission source of plane CNT (carbon nano-tube) of function admirable.
Embodiment 8:
Present embodiment adopts the Fe-Al-Cr fibre knitting cloth as substrate, and the area of Fe-Al-Cr fibre knitting cloth is 2 * 2cm
2, fibre diameter is 15 μ m, the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL decane, adding 20mg phthalocyanine cobalt, 3.5g average particulate diameter are about magnesia powder and the 6mg sulfolane of 0.7mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 1000W, and the sonicated time is 10 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(3) in Purification of Carbon Nanotubes and shearing step and the condition, except that using nitric acid corrosion oxidation magnesium and catalyst granules, all the step 4 with embodiment 4 is identical for other.
(4) preparation of nano carbon pipe isopropanol suspension: measure the 100mL isopropyl alcohol, add 22.5mg with step (2) and (3) prepare from pure CNT (carbon nano-tube) and 40mg Mg (NO
3)
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the Fe-Al-Cr fibre knitting cloth, stainless steel substrates just very, the spacing of two electrodes is 15cm, and voltage is 1000V, and electrophoresis time is 10 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the Fe-Al-Cr fibre knitting cloth securely by electrophoresis process, obtains the compound field emission source of plane CNT (carbon nano-tube) of function admirable.
Embodiment 9:
Present embodiment adopts Fe-Al-Cr fibrage rope as substrate, and the length of fibrage rope is 15cm, and fibre diameter is 20 μ m, and the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL paraxylene, adding 78.4mg iron pentacarbonyl, 4g average particulate diameter are about magnesia powder and the 20.6mg diphenyl propenyl borine of 0.9mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 400W, and the sonicated time is 15 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(3) in Purification of Carbon Nanotubes and shearing step and the condition, except that using nitric acid corrosion oxidation magnesium and catalyst granules, other is all identical with embodiment 4.
(4) preparation of nano carbon pipe dimethyl formamide suspension: measure the 100mL dimethyl formamide, add high-purity nm carbon pipe and the 3mg MgCl of 6mg with step (2) and (3) preparation
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 3): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein positive pole is that radius is metal (stainless steel) cylinder of 1.5cm, Fe-Al-Cr fibrage rope negative pole is positioned at the axial location of cylinder type positive pole, voltage across poles is 80V, and electrophoresis time is 2 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the Fe-Al-Cr fibrage rope securely by electrophoresis process, obtains the compound field emission source of linear nano carbon tube of function admirable.
Embodiment 10:
Present embodiment adopts nickel fibrage rope as substrate, and the length of fibrage rope is 6cm, and fibre diameter is 10 μ m, and the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL dimethyl formamide, adding 28.5mg phthalocyanine cobalt, 4.5g average particulate diameter are about silica powder and the 0.76mg triethyl phosphate of 5mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 16kHz, ultrasonic power are 200W, and the sonicated time is 30 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(3) in Purification of Carbon Nanotubes and shearing step and the condition, except that using hydrofluoric acid corrosion oxidation silicon and catalyst granules, other is all identical with embodiment 4.
(4) preparation of nano carbon pipe dimethyl formamide suspension: measure the 100mL dimethyl formamide, add high-purity nm carbon pipe and the 45mg NaOH of 1mg with step (2) and (3) preparation; Therefore, CNT (carbon nano-tube) is electronegative in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 3): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein radius is that metal (stainless steel) cylinder of 2cm links to each other with the negative pole of DC power supply, and the nickel fibrage rope that is positioned at the axial location of cylinder type negative pole links to each other with the positive pole of DC power supply; Voltage across poles is 100V, and electrophoresis time is 1 minute.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the nickel fibrage rope securely by electrophoresis process, obtains the compound field emission source of linear nano carbon tube of function admirable.
Embodiment 11:
Present embodiment adopts the nickel fibre knitting cloth as substrate, and the area of nickel fibre knitting cloth is 2 * 2cm
2, fibre diameter is 15 μ m, the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL naphthalane, adding 39mg iron pentacarbonyl, 5g average particulate diameter are about magnesia powder and the 18mg triphenyl borine of 4mm.
(2) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 500W, and the sonicated time is 15 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(3) in Purification of Carbon Nanotubes and shearing step and the condition, except that using hydrofluoric acid corrosion oxidation silicon and catalyst granules, all the step 4 with embodiment 4 is identical for other.
(4) preparation of nano carbon pipe alcohol suspension: measure 100mL ethanol, add high-purity nm carbon pipe and the 1mg MgCl of 4mg with step (2) and (3) preparation
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(5) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the nickel fibre knitting cloth, stainless steel substrates just very, and the spacing of two electrodes is 4cm, and voltage is 200V, and electrophoresis time is 6 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the nickel fibre knitting cloth securely by electrophoresis process, obtains the compound field emission source of plane CNT (carbon nano-tube) of function admirable.
Embodiment 12:
Present embodiment adopts the aluminum fiber woven cloth as substrate, and the area of aluminum fiber woven cloth is 2 * 2cm
2, fibre diameter is 5 μ m, the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron beam evaporation Nb film: deposited by electron beam evaporation method evaporation on above-mentioned aluminum fiber woven cloth is thick to be the Nb film of 30nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and aluminum fiber substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL dimethyl formamide, adding 51mg nickel carbonyl, 1.5g average particulate diameter are about silicon oxide powder and the 3.2mg sulfolane of 3mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 300W, and the sonicated time is 25 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(4) in Purification of Carbon Nanotubes and shearing step and the condition, except that using hydrofluoric acid corrosion oxidation silicon and catalyst granules, all the step 4 with embodiment 4 is identical for other.
(5) preparation of nano carbon pipe methanol suspension: measure the 100mL isopropyl alcohol, add high-purity nm carbon pipe and the 10mgAlCl of 2.5mg with step (3) and (4) preparation
3Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(6) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the aluminum fiber woven cloth of plating Nb, stainless steel substrates just very, the spacing of two electrodes is 6cm, and voltage is 300V, and electrophoresis time is 8 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the aluminum fiber woven cloth of plating Nb securely by electrophoresis process, obtains the compound field emission source of plane CNT (carbon nano-tube) of function admirable.
Embodiment 13:
Present embodiment adopts copper fibrage rope as substrate, and the length of fibrage rope is 10cm, and fibre diameter is 10 μ m, and the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron beam evaporation Fe film: deposited by electron beam evaporation method evaporation on above-mentioned copper fibrage rope is thick to be the Fe film of 50nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and copper fibrous substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL dimethyl formamide, adding 7.4mg ferrocene, 1g average particulate diameter are about alumina powder and the 4.1mg triethyl phosphate of 3mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 30kHz, ultrasonic power are 800W, and the sonicated time is 10 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(4) Purification of Carbon Nanotubes is all identical with embodiment 4 with condition with the shearing step.
(5) preparation of nano carbon pipe water supernatant liquid: measure the 100mL deionized water, add high-purity nm carbon pipe and the 0.5mg Mg (NO of 0.05mg with step (3) and (4) preparation
3)
2Therefore, CNT (carbon nano-tube) is electronegative in the suspension of being prepared.
(6) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 3): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein positive pole is that radius is metal (stainless steel) cylinder of 3cm, be positioned at the axial location of cylinder type positive pole as the copper fibrage rope of the plating Fe of negative pole, voltage across poles is 150V, and electrophoresis time is 5 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the copper fibrage rope of plating Fe securely by electrophoresis process, obtains the compound field emission source of linear nano carbon tube of function admirable.
Embodiment 14:
Present embodiment adopts the copper fibre knitting cloth as substrate, and the area of copper fibre knitting cloth is 2 * 2cm
2, fibre diameter is 20 μ m, the step of making the compound field emission source of CNT (carbon nano-tube) on this substrate is as follows:
(1) electron beam evaporation W film: deposited by electron beam evaporation method evaporation on above-mentioned copper fibre knitting cloth is thick to be the W film of 10nm, in order to strengthen the adhesion between CNT (carbon nano-tube) and copper fibrous substrate.
(2) preparation of CNT (carbon nano-tube) organic growth liquid: measure the 50mL decane, adding 85mg phthalocyanine cobalt, 0.5g average particulate diameter are about alumina powder and the 0.27mg thiophene of 2mm.
(3) CNT (carbon nano-tube) phonochemistry synthetic (referring to Fig. 1): the beaker that will fill above-mentioned organic growth liquid is put into ice bath, and inserting ultrasonic probe then, to carry out sonicated-supersonic frequency be that 20kHz, ultrasonic power are 300W, and the sonicated time is 30 minutes; After sonicated, organic solution is carried out centrifugation and filtration treatment, obtain containing the solid product of CNT (carbon nano-tube).
(4) all the step 4 with embodiment 4 is identical with condition with shearing step for Purification of Carbon Nanotubes.
(5) preparation of nano carbon pipe alcohol suspension: measure 100mL ethanol, add high-purity nm carbon pipe and the 1.5mgMgCl of 0.25mg with step (3) and (4) preparation
2Therefore, CNT (carbon nano-tube) is positively charged in the suspension of being prepared.
(6) CNT (carbon nano-tube) electrophoretic deposition (referring to Fig. 2): in the CNT (carbon nano-tube) suspension for preparing, insert two electrodes, wherein negative pole is the copper fibre knitting cloth of plating Fe, stainless steel substrates just very, the spacing of two electrodes is 7cm, and voltage is 400V, and electrophoresis time is 9 minutes.Under above-mentioned electrophoretic deposition condition, CNT (carbon nano-tube) is deposited on the copper fibre knitting cloth of plating Fe securely by electrophoresis process, obtains the compound field emission source of plane CNT (carbon nano-tube) of function admirable.
Claims (10)
1. compound field emission source of CNT (carbon nano-tube), form by substrate and the nano-sized carbon periosteum that on substrate, deposits as the electronic field emission source, it is characterized in that, described substrate is the conductive fiber braid, described braid comprises kernmantle or woven cloth, and the fiber diameter range of this braid is 1～20 μ m.
2. by the compound field emission source of the described CNT (carbon nano-tube) of claim 1, it is characterized in that, the conductive fiber of described conductive fiber braid comprises carbon fiber and iron, nickel, aluminium, copper fiber or their alloy fiber, and described ferroalloy fiber is Fe-Al-Cr alloy fiber or stainless steel fibre.
3. method for preparing the compound field emission source of CNT (carbon nano-tube) may further comprise the steps:
(a) preparation of nano carbon pipe organic growth liquid: organic growth liquid is made up of organic solvent, organic magnesium-yttrium-transition metal compound and carrier granular; The molar concentration of transiting group metal elements is 2 * 10 in the growth-promoting media
-4Mol/L～2 * 10
-2Mol/L, the addition of carrier particles is 10～100g/L;
(b) phonochemistry of CNT (carbon nano-tube) growth: under normal temperature and condition of normal pressure, organic growth liquid to step (a) preparation carries out sonicated, make organic growth liquid generation phonochemical reaction, organic growth liquid after the sonicated is carried out centrifugation and filtration, thereby obtain containing the solid product of CNT (carbon nano-tube);
(c) preparation of nano carbon pipe suspension: suspension is by water or organic solvent, form with phonochemistry method synthetic CNT (carbon nano-tube) and " charged body "; The content range of CNT (carbon nano-tube) is 1～1000mg/L, and " charged body " comprises MgCl
2, Mg (NO
3)
2, AlCl
3Or NaOH, the concentration range of " charged body " is 0.01～1g/L in suspension;
(d) electrophoretic deposition of CNT (carbon nano-tube): in the container that fills CNT (carbon nano-tube) suspension, insert two electrodes, one of them electrode is the conductive fiber braid, the entrained opposite polarity of its polarity and CNT (carbon nano-tube), two distance between electrodes are 1～15cm, voltage is 1～1, and 000V, electrophoresis time are 0.5～10 minute, CNT (carbon nano-tube) deposits on the conductive fiber braid by electrophoresis process under External Electrical Field, forms the compound field emission source of CNT (carbon nano-tube).
4. by the compound field emission source method of the described preparation CNT (carbon nano-tube) of claim 3, it is characterized in that, in described CNT (carbon nano-tube) organic growth liquid, also can add the surfactant that comprises nonmetalloid S, P or B; Described surfactant comprises thiophene, sulfolane, triethyl phosphate, diphenylprop thiazolinyl borine or triphenyl borine; The molar concentration of surfactant is 2 * 10 in the solution
-5Mol/L～2 * 10
-3Mol/L.
5. by the compound field emission source method of the described preparation CNT (carbon nano-tube) of claim 3, it is characterized in that, in described electrophoretic deposition step (d), when the conductive fiber braid is carbon, aluminium or copper fibrous braid, for improving the bonding force of electrophoretic deposition layer and substrate, need carbide former Fe, Ti, Zr, V, Nb, Mo or the W film of the about 1-50nm of first deposit thickness on above-mentioned carbon, aluminium or copper fibrous braid.
6. by the described method for preparing the compound field emission source of CNT (carbon nano-tube) of claim 3, it is characterized in that, before preparation of nano carbon pipe suspension, adopt the impurity in purifying and shearing step removal step (b) the gained solid product, obtain length controlled and relative homogeneous high purity CNT (carbon nano-tube), thereby help improving the field transmitting uniformity and the stability of compound field emission source, described purifying and shearing step are as follows:
(1) utilizes the ultrasonic dispersion technology of surface activity, carbon-containing impurities is peeled off from the CNT (carbon nano-tube) surface;
(2) adopt hydrochloric acid, sulfuric acid or nitric acid to remove aluminium oxide, magnesium oxide and catalyst granules; Adopt hydrofluoric acid to remove silica and catalyst granules;
(3) adopt the selective oxidation treatment process, comprise diluted acid circumfluence method and air oxidation process, remove the carbon-containing impurities in the product, obtain high-purity nm carbon pipe;
(4) by the sonochemistry etching process in acid solution, CNT (carbon nano-tube) is sheared the length and the uniformity thereof of control CNT (carbon nano-tube).
7. by the described method for preparing the compound field emission source of CNT (carbon nano-tube) of arbitrary claim in the claim 3,4,5 or 6, it is characterized in that, prepare the organic solvent of described CNT (carbon nano-tube) organic growth liquid, comprise paraxylene, decane, naphthalane or dimethyl formamide.
8. by the described method for preparing the compound field emission source of CNT (carbon nano-tube) of arbitrary claim in the claim 3,4,5 or 6, it is characterized in that described organic magnesium-yttrium-transition metal compound comprises transiting group metal elements Fe, Ni, Co or Mo; Organic magnesium-yttrium-transition metal compound comprises ferrocene, iron pentacarbonyl, nickel carbonyl, phthalocyanine cobalt, hexacarbonylmolybdenum, and they can be dissolved in the organic solvent that is used for preparation of nano carbon pipe organic growth liquid.
9. by the described method for preparing the compound field emission source of CNT (carbon nano-tube) of arbitrary claim in the claim 3,4,5 or 6, it is characterized in that, described carrier granular comprises having chemically inert silica, aluminium oxide or magnesium oxide powder, and the powder particle diameter is 0.5～5mm.
10. by the described method for preparing the compound field emission source of CNT (carbon nano-tube) of arbitrary claim in the claim 3,4,5 or 6, it is characterized in that, the operating frequency of organic growth liquid being carried out the supersonic source of sonicated is 15～32KHz, power is 100～2000W, and the time of sonicated is 5～40 minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7867468B1 (en) * | 2008-02-28 | 2011-01-11 | Carbon Solutions, Inc. | Multiscale carbon nanotube-fiber reinforcements for composites |
| US8449858B2 (en) | 2009-06-10 | 2013-05-28 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
| US8454923B2 (en) | 2009-06-10 | 2013-06-04 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
| CN104576261A (en) * | 2014-12-31 | 2015-04-29 | 中国科学院深圳先进技术研究院 | Cold cathode X-ray tube manufacturing process based on carbon nano-tubes |
| CN108878233A (en) * | 2018-06-19 | 2018-11-23 | 大连理工大学 | A kind of preparation method of the carbon-fiber cathode for electron beam transmitting |
-
2006
- 2006-03-28 CN CNB2006100663062A patent/CN100514529C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7867468B1 (en) * | 2008-02-28 | 2011-01-11 | Carbon Solutions, Inc. | Multiscale carbon nanotube-fiber reinforcements for composites |
| US8449858B2 (en) | 2009-06-10 | 2013-05-28 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
| US8454923B2 (en) | 2009-06-10 | 2013-06-04 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
| CN104576261A (en) * | 2014-12-31 | 2015-04-29 | 中国科学院深圳先进技术研究院 | Cold cathode X-ray tube manufacturing process based on carbon nano-tubes |
| CN104576261B (en) * | 2014-12-31 | 2017-03-15 | 中国科学院深圳先进技术研究院 | A kind of processing technology of the cold cathode X-ray tube based on CNT |
| CN108878233A (en) * | 2018-06-19 | 2018-11-23 | 大连理工大学 | A kind of preparation method of the carbon-fiber cathode for electron beam transmitting |
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| Publication number | Publication date |
|---|---|
| CN100514529C (en) | 2009-07-15 |
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