production of carbon nanotubes
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Lecture 2. Production of carbon nanotubes. Methods:. Pyrolysis of hydrocarbons in the presence of metal catalysts (1950 - present). Main products: multi-walled carbon nanotubes . Catalysts: Fe, Co, Ni Temperature: 800 -1200 C - PowerPoint PPT PresentationTRANSCRIPT
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Production of carbon nanotubes
Lecture 2
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Methods:
1. Pyrolysis of hydrocarbons in the presence of metal catalysts (1950 - present)
Main products: multi-walled carbon nanotubes.Catalysts: Fe, Co, Ni Temperature: 800 -1200 CPrecursors: C2H2, CH4 (gases), benzene (solution), camphour (solid)
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Experimental set up
a. One-step process (gas precursors)
Furnace 800-1200 C
H2/
Ar
C2H
2, o
r C
H4
catalysts
CNTs grown in substrateQuartz tube or ceramic tube
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Furnace 800-1200 C
catalysts
H2/
Ar
benzene
One-step process (solution precursors)
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b. Two step-process (solid precursors)
150-300 C 800-1200 C
catalystscamphour
Ar/
H2
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150-300 C 800-1200 C
ferrocene
Ar/
H2
Two step-processMetallic-organics as precursors: Ferrocene (五環鐵 )
Fe
CNTs deposited on tube walls
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Random arrangement of multi-walled CNTs
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He or (Ar) atmosphere
Anode (+) Cathode (-)
20- 35 V, 70-120 A
Arc temperature 2500-3500 C
2. DC Arc discharge of graphite (1990-present)
Products: Fullerenes and multi-walled CNTs
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See website at http://tw.youtube.com/watch?v=8N79nlhwcgM&feature=related
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正極消耗
負極長出銀灰色碳積物稱為 (carbon deposit)
真空腔壁層積碳灰 , 稱為 carbon soot: fullerenes 藏于 soot 中
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分離
Side view Front view Cut open
Multi-walled CNTs
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Carbon deposit at cathode
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Hollow anode
cathode
Filling with Fe, Co, Ni or others to produce single-walled CNTs
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陽極 陰極腔體
原始煤灰5cm
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正極消耗
負極長出銀灰色碳積物稱為 (carbon deposit)
真空腔壁層積碳灰 , 稱為 carbon soot: fullerenes 及 SWNTs 藏于 soot 中
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Filling with B, B2O3 or boron compounds to produce B-doped multi-walled CNTs
anode
B
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Filling with Ta, Ta2O5 or Tatanlum compounds to produce encapsulated TaC multi-walled CNTs
anode
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3. Laser ablation of Co-Ni-graphite (1995-present)
Products: single-walled carbon nanotubes
Co-Ni-graphite
1200 C
furnace
Laser beam cooler
SWNTs found on cooler
He
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4. Electrolysis of graphite in molten ionic salts (1995-present)
Product: multi-walled CNTs, low melting points metals (Sn, Pb, Bi) encapsulated CNTs
furnace
Graphite crucible
Graphite rod
LiCl, KCl, NaCl
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5. others, derivatives of pyrolysis, e.g. plasma CVD, MOCVD,… etc
Products: variety of CNTs, including SWNTs, MWNTs
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Improved techniques on nanotube growth
Substrate and catalyst modification
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改變金屬催化劑形態 (簡單矩陣 )
Science, 283,512,1999
Thin film of Fe
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比較複雜碳管矩陣
Chem.Phys.Lett, 371, 433, 2003 APL. 79, 3155, 2001
APL, 79, 1534, 2001
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Nature, 416, 495, 2002.
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碳管整齊排列之意義為何 ?1.提昇場發射性能 (field emission) ? (not true, because threshold field and turn-on-voltage is even higher than random arranged CNTs)
2. 陣列成長時 , 碳管之結晶性 , 結構 或 長度 , 直徑比雜亂成長 較為均勻一致 (possibly true, at least tube length and diameter are rather uniform than random growth of CNTs on substrate).
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Growth mechanisms of CNTs
Characteristics of CNT growth in arc discharge process1. No catalyst --- multi-walled CNTs (fact)
2. Electric field driven growth (not certain ?) E
+ -
5-10V/m
3. High temperature (fact)
4. Less defects on CNTs and high degree of graphitization (high crystallinity) (Fact).
Arc-CNTs
Pyrolysis-CNTs
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5. CNT length is limited to 5-15 m, tube diameter is similar to pyrolysis grown CNTs (fact)
6. open-ended growth (reasonable)
wrongPossibly right
Open-endBoth-end growth
7. Carbon ions exchange in arc zone (C+ > C-)
C+ C++ -C-
C-
8. CNT growth in arc discharge requires buffer gas (He, Ar, 300-500 torr). In a vacuum tube cannot grow (Fact).
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9. Probability of hexagon formation is higher than that of pentagons in arc process, so CNT growth continues, otherwise pentagons lead to tube closure. When tube closure occurs tube growth stops. (fact)
Incoming ions
2
3
1
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Growth mechanisms of CNTs in pyrolysis process
1. Metal catalysts are needed, metal particles are always at tube tips (fact).
2. H2 is always needed (not true), because pyrolysis of C60 can also produce CNTs in Ar or N2 flow.
3. Lower production temperature compared with arc discharge, so CNTs are defective structures (fact).
4. Two types of growths have been argued since 1970 by M. Endo and RTK Baker
5. Lift-off growth and rooting growth
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Modification of Baker’s model
Fe
Room temp800-1200C
C2H2 C2H2
Atoms strongly vibrate in lattice
C2H2 C2H2
dropletH
Cold Fe
Hot Fe
C
Migration of C through Fe droplet
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When C diffuses through Fe, carbidic species formCarbidic species: Intermediate phase of carbide
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Baker’s model cannot explain why CNTs are hollow structure
Migration of C through Fe droplet
solid structure
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Lift-off growth
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Rooting growth
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None-sense mechanisms on CNT growth 極其無聊之碳管成長機制
1. Scooter mechanism by rice group
CCo
growth
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2. Co-C60 catalyzed growth in arc process
CoC
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Why they proposed these none sense mechanisms?
Because at a time they did not see metal articles at tube tips!
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Particularly, the Co-C60 catalyzed growth model was proposed based on two wrong images.
Image 1
Image 2
1.1-1.2Å7Å1.1-1.2Å
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True is finally found by Rice group itself Chem.Phys.Lett, 260, 471, 1996
Endo and Baker’s models