CN101456074B - Method for filling carbon nano tube with magnetic nano metal iron particles - Google Patents
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Abstract
The invention belongs to the technical field of preparation and application of nano composite material, and in particular relates to a method for preparing a magnetic nano metallic iron particle/carbon nano tube functional composite material. The invention discloses a method for filling a carbon nano tube with magnetic nano metallic iron particles. The method comprises the following steps: carrying out refluxing treatment on the carbon nano tube in concentrated nitric acid, introducing functional groups such as carbonyl, hydroxyl, carboxyl and the like on the surface of the carbon nano tube, carrying out ultrasonic dispersion and electromagnetic mixing on the treated carbon nano tube in aqueous solution of bivalent ferric salt, filling the bivalent ferric salt in the carbon nano tube through capillary action, thermally treating the carbon nano tube at inert atmosphere, decomposing the bivalent ferric salt filled inside the carbon nano tube into ferric oxide, and reducing the ferric oxide into the magnetic nano metallic iron particles by hydrogen to obtain the composite material for filling the magnetic nano metallic iron particles into the carbon nano tube, wherein the magnetic nano metallic iron particles can be filled in the carbon nano tubes the calibers of which are 10 to 100 nanometers and which have different structures, and the carbon nano tubes with different calibers as templates can accurately control the size of the magnetic nano metallic iron particles. The method has the advantages of simple process and good controllability, can make the magnetic nano metallic iron particles evenly filled in the carbon nano tube with high filling rate, and is convenient for industrialized production; and the prepared nano magnetic composite material has good application prospect in the fields of high-density magnetic recording materials, wave-absorbing materials, electromagnetic shielding materials, nuclear magnetic resonance imaging materials.
Description
Technical field
The present invention relates to the preparation method of nano composite material, be specifically related to a kind of method of filling carbon nano tube with magnetic nano metal iron particles.
Background technology
Magnetic composite is widely used in preparing the high density magnetic recording material, be used for data and store, and be used to prepare absorbing material, electromagnetic shielding material, xerography with ink, wide band transformer, noise filter, medically directed thermal-arrest treatment tumour and targeted delivery of drugs etc.
Since CNT is found, owing to have a lot of novel unique characteristics, aspect a lot of, have a wide range of applications, the researcher has given great attention.Studies show that, the carbon nano tube compound material of CNT being filled preparation has shown excellent more physics and chemical characteristic, as better optical property, electric conductivity, catalytic performance, magnetic property, absorbing property and capability of electromagnetic shielding etc., have more wide application prospect, thereby become a focus of current research.
The filling of CNT is to utilize this nanometer space of hollow tube to carry out the nanoscale reaction, form nano composite material, construct the effective means of nano-component and preparation 1-dimention nano lead, can realize by following several approach: the original position completion method in (1) building-up process, nano metal or metal carbides are filled in the CNT in the growth course of CNT, when being equipped with CNT with the arc discharge legal system, Gd, La, Mn, Nd, Ta, Mo and carbide thereof [Liu MQ, et al.Carbon, 1995,33 (6): 749], and Cr, Dy, Yb, Gd, Pd, Fe, Co, Ni and carbide thereof [Guerret PC, et al.Nature, 1994,372:761] successfully be filled in CNT inside; Also can in the carbon nano tube growth process, be filled in CNT inside [Che RC, et al.Advanced Materials, 2004,16 (5): 401 to particles such as nanometer Fe, Co, Ni or nano wire by chemical vapour deposition technique; Bao CNR, et al.Chemical Communication, 1998,15:1525; Bao JC, et al.Advanced Materials, 2002,14 (20): 1483].(2) physics is filled, this method is that CNT is filled the metal high annealing with desire, melt metal is filled in the CNT because of capillarity, the Rb of low surface tension, S, Se, Cs etc. can be filled in CNT inside [Dujardin E, et al.Science, 1994,265:1850].(3) chemistry is filled, because the physics completion method only is applicable to the material of some low surface tensions usually, therefore for some high capillary metals and transition metal, the chemistry completion method is present comparatively desirable a kind of method, the chemistry filling can be divided into dry method fusion filling and wet method is filled two kinds, it mainly is to utilize the CNT of metal and sealing hot altogether under oxidizing atmosphere that the dry method fusion is filled, metal takes place, chemical reaction between oxygen and the carbon, generate the compound of low surface tension, thereby be filled into the hollow tube of CNT by capillarity, metallic lead has been filled in CNT inside [Ajayan PM et al.Nature by this method, 1993,361:333].It is with CNT and the reactant aqueous solution that is dissolved with slaine that wet chemistry method is filled, and aqueous metal salt is filled and entered in the CNT in the CNT opening, fills by wet chemistry method, and Cr has been filled in CNT inside
2O
3Deng compound [Mittal J et al.Chemical Physics Letters, 2001,339 (5-6): 311], and Ag particle and PbO
2Deng material [Ugarteet al.Applied Physics A 67 (1): 101-105].
CNT causes the extensive concern of scientific circles with its excellent electricity, engineering properties, microwave absorbing property and unique vestibule structure; with the nano container of CNT as the second phase material; especially as the nano container of filling the nano metal material; has good application prospects; because nanometer ferromagnetic metal (as Fe, Co, Ni etc.) is than being easier to oxidation; fill it in the CNT; by the protective effect of CNT, can improve the oxidation resistance of nanometer magnetic metal particle greatly.The method that is adopted with magnetic Nano metallic iron filling carbon nano-pipe is mainly the ferrocene volatility process, and adopting ferrocene is carbon source and source of iron, [Karmakar S, et al.Journal of Applied Physics, 2005,97 (5): 54306; Rao CNR, et al.ChemicalCommunications, 1998,15:1525], but the loading of this metallic iron is very low.Template also is a kind of method [the Boa JC that fills the magnetic Nano metallic iron in CNT, et al.Advanced Materials, 2002,14 (20): 1483], this method at first needs to synthesize the template of nano-scale, reaction also will be removed these templates after finishing, and technology is very complicated.In addition, CNT and ferrocene mixture are heated under nitrogen atmosphere, also can be filled in [Lin HY in the CNT to nanometer metallic iron, et al.Materials Letters, 2007,61 (16): 3547], but the filling rate of nanometer metallic iron is very low.In CNT, evenly fill the magnetic Nano metal iron particles with wet chemistry method, in being the CNT of 10-100 nanometer different structure, caliber fills the magnetic Nano metal iron particles, adopt the particle diameter of the CNT of different tube diameters as template control magnetic Nano metal iron particles, preparation filling carbon nano tube with magnetic nano metal iron particles composite is not seen document and patent report as yet.
Based on above-mentioned consideration, the present invention intends passing through wet chemistry method, it is simple to develop a kind of technology, the preparation method that controllability is good, realize of the even filling of magnetic Nano metal iron particles, make and have high fill-ratio and the controlled magnetic Nano metallic iron filling carbon nano-pipe composite of particle diameter in CNT inside.
Summary of the invention
The objective of the invention is to disclose the method for the filling carbon nano tube with magnetic nano metal iron particles that a kind of technology is simple, controllability is good, to satisfy the needs of relevant field development.
One of purpose of the present invention provides a kind of inner carbon nano tube compound material of filling the magnetic Nano metal iron particles.
Another object of the present invention is to propose a kind of employing wet chemistry method evenly to fill the magnetic Nano metal iron particles in CNT, in being the CNT of 10-100 nanometer different structure, caliber fills the magnetic Nano metal iron particles, adopt the particle diameter of the CNT of different tube diameters as template control magnetic Nano metal iron particles, the method for the carbon nano tube compound material of magnetic Nano metal iron particles is filled in preparation.
Filling magnetic Nano metal iron particles carbon nano tube compound material of the present invention, the described material that is filled is the multi-walled carbon nano-tubes with different-diameter, described filler is the magnetic Nano metal iron particles, the magnetic Nano metal iron particles particle diameter of described filling is the 2-40 nanometer, and the diameter of one-dimensional nano-composite material is the 10-100 nanometer.
The method of filling carbon nano tube with magnetic nano metal iron particles of the present invention comprises the steps:
(1) CNT is joined in the red fuming nitric acid (RFNA) (68%), ultrasonic dispersion 30 minutes, 120-130 ℃ of condensing reflux reaction 20-24 hour, temperature with reaction mixture drops to 20-30 ℃ then, use membrane filtration, and with the deionized water cleaning and filtering to pH be 6.5-7, obtain the CNT of functional groups such as surperficial carbonylate, hydroxyl, carboxyl, in the air 60 ℃ the oven dry 24 hours;
The CNT of being addressed is selected from four kinds of multi-walled carbon nano-tubes that caliber is respectively 10-20 nanometer, 20-40 nanometer, 40-60 nanometer, 60-100 nanometer;
The filter opening diameter range of the filter membrane of being addressed is 0.5-1 μ m;
(2) divalent iron salt is made into the aqueous solution that concentration is 20-40%, the CNT of functional groups such as the surperficial carbonylate that step (1) is obtained, hydroxyl, carboxyl is put into the aqueous solution of divalent iron salt, ultrasonic dispersion 30min, electromagnetic agitation 24 hours, use membrane filtration, dried 12 hours for 60 ℃ in the air, obtain inner CNT of filling divalent iron salt;
The divalent iron salt of being addressed is ferrous sulfate or ferrous nitrate;
The CNT of the inside filling divalent iron salt that (3) step (2) is obtained is put into quartz boat, puts into the quartz ampoule reative cell, the quartz ampoule reative cell is placed in the tube type resistance furnace again;
(4) the quartz ampoule reative cell to the described good seal of step (3) vacuumizes, in the quartz ampoule reative cell, feed nitrogen again, simultaneously the temperature of reative cell is warming up to 100 ℃ from room temperature with the speed of 4-6 ℃/min, and at 100 ℃ of constant temperature 2-3 hours, speed with 4-6 ℃/min continues to be warming up to 550-600 ℃ then, and the divalent iron salt of filling in the CNT was decomposed into iron oxide finishing heat treatment in constant temperature 4-6 hour under this temperature;
The flow of being addressed that feeds nitrogen in the quartz ampoule reative cell is 100mL/min;
(5) speed with 5-10 ℃/min is warming up to 700-750 ℃, the nitrogen flow of set-up procedure (4) is to 200-300mL/min, and the hydrogen of feeding 100-300mL/min, in order to be the magnetic Nano metallic iron, react after 3-5 hour stop supplies hydrogen with iron oxide reduction, reduce nitrogen flow to 100mL/min, quartz ampoule is cooled to room temperature in nitrogen atmosphere, stop supplies nitrogen obtains inner CNT of filling the magnetic Nano metal iron particles.
The particle diameter of the magnetic Nano metal iron particles of filling in the CNT of being addressed is the 2-40 nanometer.
Basic principle of the present invention is such: CNT is done condensing reflux and is handled in red fuming nitric acid (RFNA), introduce functional groups such as carboxyl, hydroxyl, carbonyl in carbon nano tube surface, the wetability of the CNT and the divalent iron salt aqueous solution can improve in these functional groups, be filled in CNT inside by the capillarity divalent iron salt aqueous solution, be decomposed into iron oxide through the Overheating Treatment divalent iron salt, is the magnetic Nano metallic iron with hydrogen with iron oxide reduction, is filled in CNT inside.
The characteristics of the method for filling carbon nano tube with magnetic nano metal iron particles provided by the invention are: the one, adopt the wet chemistry method in CNT, to fill the magnetic Nano metal iron particles, realized the magnetic Nano metal iron particles in CNT even filling and high filling rate; The 2nd, the CNT of employing different tube diameters can be controlled the particle diameter of magnetic Nano metal iron particles more exactly as template; The 3rd, can in being the CNT of 10-100 nanometer different structure, caliber fill the magnetic Nano metal iron particles.
Method provided by the invention is simple to operation, the controllability height, and the specific yield height is beneficial to generation in enormous quantities.Have a good application prospect in fields such as high density magnetic recording material, absorbing material, electromagnetic shielding material, Magnetic resonance imaging, bio-medical materials.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the filling carbon nano tube with magnetic nano metal iron particles of embodiment 1 preparation.
Fig. 2 is the transmission electron microscope photo of the filling carbon nano tube with magnetic nano metal iron particles of embodiment 2 preparations.
Fig. 3 is the transmission electron microscope photo of the filling carbon nano tube with magnetic nano metal iron particles of embodiment 3 preparations.
Fig. 4 is the transmission electron microscope photo of the filling carbon nano tube with magnetic nano metal iron particles of embodiment 4 preparations.
The specific embodiment
Embodiment 1
(1) at ambient temperature, with the 5g diameter is that the CNT of 10-20 nanometer joins (68%) in the 250ml red fuming nitric acid (RFNA), ultrasonic dispersion 30 minutes, back flow reaction is 24 hours in 125 ℃ of oil baths, temperature with the back flow reaction mixed liquor drops to 23 ℃ then, with the membrane filtration of 0.85 μ m, and with the deionized water cleaning and filtering to pH be 6.8, obtain the CNT of functional groups such as surperficial carbonylate, hydroxyl, carboxyl, in air, dried 24 hours for 60 ℃;
(2) ferrous sulfate being made into concentration is 20% the aqueous solution, the CNT of functional groups such as the surperficial carbonylate that step (1) is obtained, hydroxyl, carboxyl is put into ferrous sulfate aqueous solution, ultrasonic dispersion 30min, electromagnetic agitation 24 hours, use membrane filtration, dried 12 hours for 60 ℃ in the air, obtain inner CNT of filling ferrous sulfate;
The CNT of the inside filling ferrous sulfate that (3) step (2) is obtained is put into quartz boat, puts into the quartz ampoule reative cell, the quartz ampoule reative cell is placed in the tube type resistance furnace again;
(4) the quartz ampoule reative cell to the described good seal of step (3) vacuumizes, in the quartz ampoule reative cell, feed nitrogen again, the flow of nitrogen is 100mL/min, simultaneously the temperature of reative cell is risen to 100 ℃ from room temperature with the speed of 4 ℃/min, and 100 ℃ of constant temperature 2 hours, speed with 5 ℃/min continues to be warming up to 550 ℃ then, and constant temperature 5 hours is to finish heat treatment under 550 ℃ temperature, and the ferrous sulfate of filling in the CNT is decomposed into iron oxide;
(5) speed with 5 ℃/min is warming up to 700 ℃, the nitrogen flow of set-up procedure (4) is to 200mL/min, and the hydrogen of feeding 100mL/min, in order to be the magnetic Nano metallic iron, react after 3 hours with iron oxide reduction, stop supplies hydrogen, reduce nitrogen flow to 100mL/min, quartz ampoule is cooled to room temperature in nitrogen atmosphere, stop supplies nitrogen, obtain inner CNT of filling the magnetic Nano metal iron particles, the particle diameter of magnetic Nano metal iron particles is the 2-6 nanometer.
Embodiment 2
(1) at ambient temperature, with the 4.5g diameter is that the CNT of 20-40 nanometer joins (68%) in the 200ml red fuming nitric acid (RFNA), ultrasonic dispersion 30 minutes, back flow reaction is 20 hours in 120 ℃ of oil baths, temperature with the back flow reaction mixed liquor drops to 24 ℃ then, with the membrane filtration of 0.85 μ m, and with the deionized water cleaning and filtering to pH be 6.5, obtain the CNT of functional groups such as surperficial carbonylate, hydroxyl, carboxyl, in air, dried 24 hours for 60 ℃;
(2) ferrous sulfate being made into concentration is 25% the aqueous solution, the CNT of functional groups such as the surperficial carbonylate that step (1) is obtained, hydroxyl, carboxyl is put into ferrous sulfate aqueous solution, ultrasonic dispersion 30min, electromagnetic agitation 24 hours, use membrane filtration, dried 12 hours for 60 ℃ in the air, obtain inner CNT of filling ferrous sulfate;
The CNT of the inside filling ferrous sulfate that (3) step (2) is obtained is put into quartz boat, puts into the quartz ampoule reative cell, the quartz ampoule reative cell is placed in the tube type resistance furnace again;
(4) the quartz ampoule reative cell to the described good seal of step (3) vacuumizes, in the quartz ampoule reative cell, feed nitrogen again, the flow of nitrogen is 100mL/min, simultaneously the temperature of reative cell is risen to 100 ℃ from room temperature with the speed of 5 ℃/min, and 100 ℃ of constant temperature 2.5 hours, speed with 6 ℃/min continues to be warming up to 570 ℃ then, and constant temperature 4 hours is to finish heat treatment under 570 ℃ temperature, and the ferrous sulfate of filling in the CNT is decomposed into iron oxide;
(5) speed with 6 ℃/min is warming up to 720 ℃, the nitrogen flow of set-up procedure (4) is to 250mL/min, and the hydrogen of feeding 200mL/min, be reduced to the magnetic Nano metallic iron in order to oxide with iron, react after 4 hours, stop supplies hydrogen, reduce nitrogen flow to 100mL/min, quartz ampoule is cooled to room temperature in nitrogen atmosphere, stop supplies nitrogen, obtain inner CNT of filling the magnetic Nano metal iron particles, the particle diameter of magnetic Nano metal iron particles is the 5-15 nanometer.
Embodiment 3
(1) at ambient temperature, with the 6g diameter is that the CNT of 40-60 nanometer joins (68%) in the 300ml red fuming nitric acid (RFNA), ultrasonic dispersion 30 minutes, back flow reaction is 22 hours in 130 ℃ of oil baths, temperature with the back flow reaction mixed liquor drops to 25 ℃ then, with the membrane filtration of 0.85 μ m, and with the deionized water cleaning and filtering to pH be 7, obtain the CNT of functional groups such as surperficial carbonylate, hydroxyl, carboxyl, in air, dried 24 hours for 60 ℃;
(2) ferrous sulfate being made into concentration is 30% the aqueous solution, the CNT of functional groups such as the surperficial carbonylate that step (1) is obtained, hydroxyl, carboxyl is put into ferrous sulfate aqueous solution, ultrasonic dispersion 30min, electromagnetic agitation 24 hours, use membrane filtration, dried 12 hours for 60 ℃ in the air, obtain inner CNT of filling ferrous sulfate;
The CNT of the inside filling ferrous sulfate that (3) step (2) is obtained is put into quartz boat, puts into the quartz ampoule reative cell, the quartz ampoule reative cell is placed in the tube type resistance furnace again;
(4) the quartz ampoule reative cell to the described good seal of step (3) vacuumizes, in the quartz ampoule reative cell, feed nitrogen again, the flow of nitrogen is 100mL/min, simultaneously the temperature of reative cell is risen to 100 ℃ from room temperature with the speed of 6 ℃/min, and 100 ℃ of constant temperature 3 hours, speed with 5 ℃/min continues to be warming up to 580 ℃ then, and constant temperature 6 hours is to finish heat treatment under 580 ℃ temperature, and the ferrous sulfate of filling in the CNT is decomposed into iron oxide;
(5) speed with 8 ℃/min is warming up to 730 ℃, the nitrogen flow of set-up procedure (4) is to 300mL/min, and the hydrogen of feeding 300mL/min, in order to be the magnetic Nano metallic iron, react after 5 hours with iron oxide reduction, stop supplies hydrogen, reduce nitrogen flow to 100mL/min, quartz ampoule is cooled to room temperature in nitrogen atmosphere, stop supplies nitrogen, obtain inner CNT of filling the magnetic Nano metal iron particles, the particle diameter of magnetic Nano metal iron particles is the 10-30 nanometer.
Embodiment 4
(1) at ambient temperature, with the 5g diameter is that the CNT of 60-100 nanometer joins (68%) in the 250ml red fuming nitric acid (RFNA), ultrasonic dispersion 30 minutes, back flow reaction is 20 hours in 130 ℃ of oil baths, temperature with the back flow reaction mixed liquor drops to 26 ℃ then, with the membrane filtration of 0.85 μ m, and with the deionized water cleaning and filtering to pH be 7, obtain the CNT of functional groups such as surperficial carbonylate, hydroxyl, carboxyl, in air, dried 24 hours for 60 ℃;
(2) ferrous nitrate being made into concentration is 40% the aqueous solution, the CNT of functional groups such as the surperficial carbonylate that step (1) is obtained, hydroxyl, carboxyl is put into ferrous nitrate aqueous solution, ultrasonic dispersion 30min, electromagnetic agitation 24 hours, use membrane filtration, dried 12 hours for 60 ℃ in the air, obtain inner CNT of filling ferrous nitrate;
The CNT of the inside filling ferrous nitrate that (3) step (2) is obtained is put into quartz boat, puts into the quartz ampoule reative cell, the quartz ampoule reative cell is placed in the tube type resistance furnace again;
(4) the quartz ampoule reative cell to the described good seal of step (3) vacuumizes, in the quartz ampoule reative cell, feed nitrogen again, the flow of nitrogen is 100mL/min, simultaneously the temperature of reative cell is risen to 100 ℃ from room temperature with the speed of 5 ℃/min, and 100 ℃ of constant temperature 2 hours, speed with 4 ℃/min continues to be warming up to 600 ℃ then, and constant temperature 5 hours is to finish heat treatment under 600 ℃ temperature, and the ferrous nitrate of filling in the CNT is decomposed into iron oxide;
(5) speed with 10 ℃/min is warming up to 750 ℃, the nitrogen flow of set-up procedure (4) is to 200mL/min, and the hydrogen of feeding 150mL/min, in order to be the magnetic Nano metallic iron, react after 4.5 hours with iron oxide reduction, stop supplies hydrogen, reduce nitrogen flow to 100mL/min, quartz ampoule is cooled to room temperature in nitrogen atmosphere, stop supplies nitrogen, obtain inner CNT of filling the magnetic Nano metal iron particles, the particle diameter of magnetic Nano metal iron particles is the 15-40 nanometer.
Claims (5)
1. the method for a filling carbon nano tube with magnetic nano metal iron particles is characterized in that, this method comprises the steps:
(1) CNT is joined in 68% red fuming nitric acid (RFNA), ultrasonic dispersion 30 minutes, 120-130 ℃ of condensing reflux reaction 20-24 hour, temperature with reaction mixture drops to 20-30 ℃ then, use membrane filtration, and with the deionized water cleaning and filtering to pH be 6.5-7, obtain the CNT of functional groups such as surperficial carbonylate, hydroxyl, carboxyl, in the air 60 ℃ the oven dry 24 hours;
(2) ferrous sulfate or ferrous nitrate are made into the aqueous solution that concentration is 20-40%, the CNT of functional groups such as the surperficial carbonylate that step (1) is obtained, hydroxyl, carboxyl is put into this aqueous solution, ultrasonic dispersion 30min, electromagnetic agitation 24 hours, use membrane filtration, dried 12 hours for 60 ℃ in the air, obtain inner CNT of filling ferrous sulfate or ferrous nitrate;
(3) the inside filling ferrous sulfate that step (2) is obtained or the CNT of ferrous nitrate are put into quartz boat, put into the quartz ampoule reative cell, the quartz ampoule reative cell are placed in the tube type resistance furnace again;
(4) the quartz ampoule reative cell to the described good seal of step (3) vacuumizes, in the quartz ampoule reative cell, feed nitrogen again, simultaneously the temperature of reative cell is warming up to 100 ℃ from room temperature with the speed of 4-6 ℃/min, and at 100 ℃ of constant temperature 2-3 hours, speed with 4-6 ℃/min continues to be warming up to 550-600 ℃ then, and the ferrous sulfate or the ferrous nitrate of filling in the CNT were decomposed into iron oxide finishing heat treatment in constant temperature 4-6 hour under this temperature;
(5) speed with 5-10 ℃/min is warming up to 700-750 ℃, the nitrogen flow of set-up procedure (4) is to 200-300mL/min, and the hydrogen of feeding 100-300mL/min, in order to be the magnetic Nano metallic iron, react after 3-5 hour stop supplies hydrogen with iron oxide reduction, reduce nitrogen flow to 100mL/min, quartz ampoule is cooled to room temperature in nitrogen atmosphere, stop supplies nitrogen obtains inner CNT of filling the magnetic Nano metal iron particles.
2. the method for filling carbon nano tube with magnetic nano metal iron particles as claimed in claim 1 is characterized in that, the filter opening diameter range of the filter membrane in the described step (1) is 0.5-1 μ m.
3. the method for filling carbon nano tube with magnetic nano metal iron particles as claimed in claim 1 is characterized in that, the flow that feeds nitrogen in the described step (4) in the quartz ampoule reative cell is 100mL/min.
4. the method for filling carbon nano tube with magnetic nano metal iron particles as claimed in claim 1 is characterized in that, the particle diameter of the magnetic Nano metal iron particles of filling in the CNT is the 2-40 nanometer.
5. as the method for each described filling carbon nano tube with magnetic nano metal iron particles of claim 1-5 item, it is characterized in that described CNT is selected from four kinds of multi-walled carbon nano-tubes that caliber is respectively 10-20 nanometer, 20-40 nanometer, 40-60 nanometer, 60-100 nanometer.
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