Moreno, Maryline (2006) Carbon nanoparticles synthesis by gas phase non-equilibrium plasma. PhD thesis Energétique, ENSMP - CEP Centre Energétique et Procédés, ENSMP.

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Abstract

This work deals with carbon nanoparticles synthesis by a gas phase non-equilibrium plasma process.

First, the literature review, devoted to carbon black and carbon nanotubes, presents the different existing gas phase processes (conventional and plasma) and the growth mechanism of these nanoparticles.

Then, the development and the set-up of the non-equilibrium plasma process, based on the establishment of low current high voltage non thermal discharges, are described.

Next, the experimental results related to the process characterisation are presented, namely : the electrical characterisation of the plasma torch without any reagent injection and the characterisation with hydrocarbon injection. This latter is based on a parametric study and mass balances (conversion rate estimated by Gas Chromatography, GC, measurements).

The synthesized carbon nanoparticules are analysed by Scanning and Transmission Electron Microscopy (SEM and TEM), X-rays diffraction and BET analysis. Two main carbon nanoparticles families are highlighted depending on their texture : (i) Nanoparticles with a concentric tendency texture such as “classic” carbon black, acetylene like carbon black and carbon hulls, (ii) Nanoparticles with isotropic texture such as “crumpled paper sheets” with high or low nanotexture and “microporous” nanoparticles. A correlation between operating conditions and nanoparticles’ structural characteristics is presented.

Finally, a chemical kinetic model allows to estimate the process reacting volume while the computational fluid dynamics models provide an evaluation of the temperature and velocity distribution and the thermal history of the particles inside the reactor.

References

[1] Schmidt-Czalowski K. , Opalinska T. , Sentek J. , Krawczyk K. , Ruszniak J. , Zielinski T. , Radomyska K. , Methane conversion into C2 hydrocarbons and carbon black in dielectric-barrier and gliding discharges, J. Adv. Oxid. Technol. , 2004, 7 (1), 39-50.

[2] Zielinski T. , Kijenski J. , Plasma carbon black – the new active additive for plastics, Composites : Part A 36, 2005, 467-471.

[3] Ravary B. , Modélisation thermique et hydrodynamique d’un réacteur plasma triphasé. Contribution à la mise au point d’un procédé industriel pour la fabrication de noir de carbone, Thèse en Energétique, Ecole des Mines de Paris, décembre 1998.

[4] Dème I. , Contribution à la modélisation de l’écoulement dans un réacteur plasma pour la fabrication de noirs de carbone, Influence du rayonnement des particules de carbone, Thèse en Energétique, Ecole des Mines de Paris, juin 2002.

[5] Fabry F. , Etude d’un procédé plasma pour la synthèse de noir de carbone structurés par pyrolyse d’hydrocarbure à haute température et caractérisation des produits, Thèse en science de l’ingénieur, université de Perpignan, juillet 1999.

[6] Gruenberber T. , Gonzalez - Aguilar J., Okuno H. , Fabry F. , Grivei E. , Probst N. , Flamant G. , Charlier J.-C. , Fulcheri L. , Tailor-made carbon nanomaterials for bulk applications via high-intensity arc plasma, Fullerenes, Nanotubes, and Carbon Nanostructures, 2005, 13 (S1), 1-9.

[7] Okuno H. , Grivei E. , Fabry F. , Gruenberger T. M. , Gonzalez-Aguilar J. , Palnichenko A. , Fulcheri F. , Probst N. , Charlier J.-C. , Synthesis of carbon nanotubes and nano-necklaces by thermal plasma process, Carbon, 2004, 42 (12-13), 2543-2549.

[1] Donnet, Bansal, Wang, Carbon black, Second Edition, Revised and Expansed, Science and Technology, ISBN : 0-8247-8975-X.

[2] Heidenreich R. D. , Hess W. M. , Ban L. L. , A test object and criteria for high resolution electron microscopy, Journal of Applied Crystallography, 1968, 1, 1-19.

[3] www.timcal.com

[4] Fauchais P. , Baronnet J. –M. , State of the art of plasma chemical synthesis of homogenous and heterogenous products, Pure and Applied Chemistry, 1980, 52, 1669-1705.

[5] Abanades S. , Badie J.-M. , Flamant G. , Fulcheri L. , Gonzalez-Aguilar J. , Gruenberger T. , Fabry F. , On-line temperature measurement in a plasma reactor for fullerene synthesis. In: Proceedings of the 7th International Thermal Plasma Processes Conference (TPP7), Strasbourg, France, June 18 – June 21, 2002, P. Fauchais ed., © 2003 by Begell House Inc., New-York, USA, ISBN 1-56700-192-0, 47-53.

[6] Fulcheri L. , Schwob Y. , Fabry F. , Flamant G. , Chibante F. P. , Laplaze D. , Fullerene production in a 3 phase AC plasma process, Carbon, 2000, 38, 797-803.

[7] Huczko A. , Lange H. , Cota-Sanchez G. , Soucy G. , Plasma synthesis of nanocarbons, EMRS, 2002, Proceedings 7th Thermal Plasma Processes, European Materials Research Society, 2002,617-631.

[8] Rose James R. , Process of and apparatus for producing carbon and gaseous fuel, Brevet N°1,352,085, 7 septembre 1920.

[9] Jakowsky Jay J. , Process and apparatus for manufacture of carbon-black unsaturated gases and hydrogen, Brevet N°1,597,277, 24 août 1926.

[10] Gonzalez-Aguilar J. , Moreno M. , Fulcheri L. , Carbon nanostructures production by gas-phase plasma processes at atmospheric pressure, Journal of Physics D : Applied Physics, à paraître 2007.

[11] Kvaerner, A method for decomposition of hydrocarbons, Brevet International, PCT, N°92/00196, 11 décembre 1992.

[12] Kvaerner, System for the production of carbon black, Brevet International, PCT, N°93/00057, 5 avril 1993.

[13] Kvaerner, Production of carbon black, Brevet International, PCT, N°93/00058, 5 avril 1993.

[14] Kvaerner, Decomposition reactor, Brevet International, PCT, N°93/00056, 5 avril 1993.

[15] Armines, Procédé et dispositif de fabrication de noir de carbone et de noir de carbone obtenu. B.F. 8000981, 1980.

[16] Procédé pour la Fabrication de Carbone 60, BF 97 07 011 du 06/06/1997. Extension PCT /EP98/03399 – WO98/55396, US 6,358,375, Australie AU 199884368, Canada CA 2293547, Japon

[17] Device and method for converting carbon containing feedstock into carbon containing materials, having a defined nanostructure, du 19/09/2000, PCT / EP01 / 10835, WO 02/24819.

[18] Carbon nanostructures and process for the production of carbon-based nanotubes, nanofibres and nanostructures, du 20/03/2003, DE103 124 94.2 WO 2004/083119. Procédé pour la fabrication de suies carbonées à microstructures définies, BF 9301554 du 05/02/1993. Extension PCT / WO94 /17908: Europe (EP 0 682 561 B1), Norvège, US 6,099,696, Canada, Japon.

[19] http://www.bellona.com / Palm T. , Buch C. , Kruse B. , Sauar E. , Bellona Report No 3 : 1999, Green Heat and Power, Eco-effective Energy Solutions in the 21st Century.

[20] Bakken J. A. , Jensen R. , Monsen B. , Raaness O. , Waernes N. , Thermal plasma process development in Norway, Pure and applied Chemistry, 1998, 70 (6), 1223-1228.

[21] Deme I. , Contribution à la modélisation de l’écoulement dans un réacteur plasma pour la fabrication de noirs de carbone, Influence du rayonnement des particules de carbone, Thèse en Energétique, Ecole des Mines de Paris, juin 2002.

[22] Fabry F. , Etude d’un procédé plasma pour la synthèse de noir de carbone structurés par pyrolyse d’hydrocarbure à haute température et caractérisation des produits, Thèse en science de l’ingénieur, université de Perpignan, juillet 1999.

[23] Fulcheri L. , Habilitation à diriger les Recherches, Nanostructures de carbone par plasma, mars 2003.

[24] Bonnet C. , Contribution à l'étude théorique de l'évaporation d'une particule sphérique d'un matériau réfractaire dans un plasma thermique. Application à l'étude du traitement thermique de réfractaires dans un lit fluidisé par un écoulement de plasma, Thèse de Doctorat d'état, Université de Perpignan, 1973.

[25] Gruenberger T. , Gonzalez-Aguilar J., Okuno H., Fabry F. , Grivei E., Probst N., Flamant G. , Charlier J. –C. , Fulcheri L. , Tailor-made carbon nanomaterials for bulk applications via highintensity arc plasma. Fullerenes, Nanotubes, and Carbon Nanostructures, vol. 13, n° S1, p. 1-9. ©2005 Marcel Dekker Inc. (revue internationale).

[26] Fulcheri L. , Gruenberger T. , Gonzalez-Aguilar J., Fabry F. , Grivei E. , Probst N. , Flamant G. , Okuno H. , Charlier J. –C. , Plasma processing of carbon nanomaterials, High Technology Plasma Processes, 2004, 8 (1), 119-138.

[27] Gruenberger T. , Gonzalez-Aguilar J., Fabry F. , Fulcheri L. , Grivei E., Probst N., Flamant G. , Okuno H. , Charlier J. –C. , Production of carbone nanotubes and other nanostructures via continuous 3-phase AC plasma processingFullerenes, Nanotubes, and Carbon Nanostructures, vol. 12, n° 3, p. 571-581. © 2004 Marcel Dekker Inc.

[28] Fulcheri L. , Probst N., Flamant G. , Fabry F. , Grivei E. , Bourrat X. , Plasma processing: a step towards the production of new grades of carbon black, Carbon, 2002, 40, 169-176.

[29] Fabry F. , Flamant G. , Fulcheri L. , Carbon black processing by thermal plasma. Analysis of the particle formation mechanism, Chemical Engineering Science, 2001, 56, 2123-2132.

[30] Fulcheri L. , Schwob Y. , Flamant G. , Comparison between new carbon nanostructures produced by plasma with industrial carbon black grades, Journal of Physics III, 1997, 7, 491-503.

[31] Fulcheri L. , Schwob Y. , From methane to hydrogen, carbon black and water, Int. J. Hydrogen Energy, 1995, 20 (3), 197-202.

[32] Ravary B. , Fulcheri L. , Flamant G. , Fabry F. , Analysis of a 3-phase A.C. plasma system, High Temp. Material Processes, 2, 1998, 245-260.

[33] Gonzalez-Aguilar J., Deme I. , Gruenberger T. , Fabry F. , Flamant G. , Ravary B. , 3D modelling of carbon black formation and particle radiation during methane cracking by thermal plasma, High Temp. Material Processes, 2003, 7, 51-56.

[34] Ravary B. , Bakken J. A. , Gonzalez-Aguilar J. , Fulcheri L. , CFD modelling of a plasma reactor for the production of nano-sized carbon materials, High Temperature Material Processes, 2003, 7, 139-144.

[35] http://www-cep.cma.fr

[36] Ravary B. , Fulcheri L. , Bakken J. A. , Flamant G. , Fabry F. , Influence of the Electromagnetic forces on momentum and heat transfert in a 3-Phase AC plasma reactor, Plasma Chemistry and Plasma Processing, Plenum Press, 1999, 19 (1), 69-89.

[37] Fincke J. R. , Anderson R. P., Hyde T. A. , Detering B. A. , Plasma pyrolysis of methane to hydrogen and carbon black, Industrial & Engineering Chemistry Research ,2002, 41, 1425 – 1435.

[38] Chen H. G. ,Zhang X. B. ,Li F. ,Xie K. C. , Formation of carbon black as a by-product of pyrolysis of light hydrocarbons in plasma jet, Proc. Annu. Int. Pittsburgh Coal Conf. , 1997, 14 (7), 12-15.

[39] Cho W. , Lee S. H. , Ju W. S. , Baek Y. , Lee J. K. , Conversion of natural gas to hydrogen and carbon black by application of plasma carbon black, Catalysis Today, 2004, 98, 633 – 638.

[40] Kim K. S. , Seo J. H. , Nam J. S. , Ju W. T. , Hong S. H. , Production of hydrogen and carbon black by methane decomposition using DC – RF hybrid thermal plasmas, IEE Transactions on plasma science, 2005, 33 (2) , 813 – 823.

[41] Probst N. , Grivei E. , Fabry F. ; , Fulcheri F. , Flamant G. , Bourrat X. , Schroder A. , Quality and performance of carbon blacks from plasma process, Rubber Chem. Technol. , 2002, 75, 891 – 905.

[42] Fulcheri L. , Schwob Y. , Flamant G. , Comparision between new carbon nanostructures produced by plasma with industrial carbon black grades, J. Phys. III France, 1997, 7, 491 – 503.

[43] Schmidt-Czalowski K. , Opalinska T. , Sentek J. , Krawczyk K. , Ruszniak J. , Zielinski T. , Radomyska K. , Methane conversion into C2 hydrocarbons and carbon black in dielectric-barrier and gliding discharges, J. Adv. Oxid. Technol. , 2004, 7 (1), 39-50.

[44] Zielinski T. , Kijenski J. , Plasma carbon black – the new active additive for plastics, Composites : Part A 36, 2005, 467-471.

[45] Bolouri K.S. , Amouroux J. , Analyse des processus de formation de noir de carbone : une corrélation entre le mécanisme de formation du noir de carbone et les calculs des équilibres chimiques hydrogène-carbone, Bulletin de la Société Chimique de France, 1983, 5-6, I.101 à I.109.

[46] http://www.onera.fr/conferences/nanotubes/index.htm, Loiseau A. , Les nanotubes, matériau du futur.

[47] Journet C. , La production de nanotubes de carbone, Thèse de doctorat, spécialité : Milieux denses et matériaux, 1998, Université de Montpellier II.

[48] Jourdain V. , Croissance catalytique séquentielle de nanotubes de carbone, Thèse de doctorat, 2003, Université Montpellier II.

[49] Harris P. J. F. , Carbon nanotubes and related structures, New materials for the twenty-first century, Cambridge university press, 1999.

[50] Su M. , Zheng B. , Liu J. , A scalable CVD method for the synthesis of single-walled carbon nanotubes with high catalyst productivity, Chemical Physics Letters, 2000, 322, 321-326.

[51] Journet C. , Maser W.K. , Bernier P. , Loiseau A. , Large - scale production of SWNT by the electric arc technique, Nature, 1997, 388, 217 – 223.

[52] Dorval D. , Foutel-Richard A. , Cau M. , Loiseau A. , Attal-Trétout B. , Cochon J. L. , Pigache D. , Bouchardy P. , Krüger V. , Geigle K. P., In situ optical analysis of the gas phase during the formation of carbon nanotubes, Journal of Nanoscience and Nanotechnology, 2004, 4 (4), 450-462.

[53] Laplaze D. , Alvarez L. , Guillard T. , Badie J. M. , Flamant G. , Carbon nanotubes : dynamics of synthesis processes, Carbon, 2002, 40, 1621 – 1634.

[54] Bacon R. , Growth, Structure, and Properties of Graphite Whiskers, Journal of Applied Physics , 1960, 31 (2), 283-290.

[55] Krätschmer W. , Lamb L. D. , Fostiropoulos K. , Huffman D. R. , Solid C60: a new form of carbon, Nature, 1990, 347, 354-358.

[56] Iijima S. , Helical microtubules of graphitic carbon, Nature, 1991, 354, 56-58.

[57] Bethune D.S. , Kiang C.H. , de Vries M.S. , Gorman G. , Savoy R. ; Vasquez J. , Beyers R, Cobalt-catalyzed growth of carbon nanotubes with single-atomic-layer walls, Nature, 1993, 363, 605.

[58] Iijima S. , Ichihashi T. , Single-shell carbon nanotubes of 1-nm diameter, Nature, 1993, 363, 603-605.

[59] Tarasov B. P. , Muradyan V. E. , Shul’ga Y.M. , Krinichnaya E. P. , Synthesis of carbon nanostructures by arc evaporation of graphite rods with Co-Ni and YNi2

catalysts, Carbon, 2003, 41 (7), 1357-1364

[60] Pacheco Pacheco M. , Synthèse des nanotubes de carbone par arc électrique, Thèse de doctorat, 2003, Université Toulouse II.

[61] Cours Aussois 2003, Nanotubes de carbone, Présentation Journet C.

[62] Ohkohchi M. , Synthesis of single-walled carbon nanotubes by AC arc discharge, Japanese Journal of Applied Physics, 1998, 38, 4158-4159.

[63] Ando Y., Zhao X., Hirahara K., Mass production of single-wall carbon nanotubes by the arc plasma jet method, Chemical Physics Letters, 2000, 323, 580-585.

[64] Huang H. , Kajiura H. , Tsutsui S. , Hirano Y. , Miyakoshi M. , Yamada A. , Ata M. , Large-scale rooted growth of aligned super bundles of single-walled carbon nanotubes using directed arc plasma method, Chemical Physics Letters, 2001, 343, 7-14.

[65] Lee S. J. , Baik H. K. , Large scale synthesis of carbon nanotubes by plasma rotating arc discharge technique, Diamond and Related Materials, 2002, 11, 914-917.

[66] Anazawa K. , Shimotani K. , Manabe C. , Watanabe H. , Shimizu M. , High-purity carbon nanotubes synthesis method by an arc discharging in magnetic field, Applied Physics Letters, 2002, 81 (4), 739-741.

[67] Kanai M. , Koshio A. , Shinohara H. , Mieno T. , Kasuya A. , Ando Y. , Zhao X. , High-yield synthesis of single-walled carbon nanotubes by gravity-free arc discharge, Applied Physics Letters, 2001, 79 (18), 2967-2969.

[68] Zhao T. , Liu Y. , Large scale and high purity synthesis of single-walled carbon nanotubes by arc discharge at controlled temperature, Carbon, 2004, 42, 2765-2768.

[69] Lange H. , Sioda M. , Huczko A. , Zhu Y. Q. , Kroto H. W. , Walton D. R. M. , Nanocarbon production by arc discharge in water, Carbon, 2003, 1617 – 1623.

[70] Okuno H. , Grivei E. , Fabry F. , Gruenberger T. M. , Gonzalez-Aguilar J. , Palnichenko A. , Fulcheri F. , Probst N. , Charlier J.-C. , Synthesis of carbon nanotubes and nano-necklaces by thermal plasma process, Carbon, 2004, 42 (12-13), 2543-2549.

[71] Hahn J. , Han H. J. , Yoo J. E. , Jung H. Y. , Suh J. S. , New continuous gas – phase synthesis of high purity carbon nanotubes by a thermal plasma jet, Carbon, 2004, 42, 877 – 883.

[72] Tian Y. , Zhang Y. , Wang B. , Ji W. , Zhang Y. , Xie K. , Coal-derivated nanotubes by thermal plasma jet, Carbon, 2004, 42, 2597-2601.

[73] Choi S. I. , Nam J. S. , Kim J. I. , Hwang T . H. , Seo J. H. , Hong S. H. , Continuous process of carbon nanotubes synthesis by decomposition of methane using an arc-jet plasma, thin Solid Films, 2006, 506-507, 244-249.

[74] Smiljanic O. , Stansfield B. L. , Dodelet J. -P. , Serventi A. , Désilets S, Gas-phase synthesis of single-wall carbon nanotubes by an atmospheric pressure plasma jet, Chemical Physics Letters, 2002, 356, 189-193.

[75] Chen C. K. , Perry W. L. , Xu H. , Jiang Y. , Phillips J. , Plasma torch production of macroscopic carbon nanotube structures, Carbon, 2003, 41, 2555-2560.

[76] Loutfy R. O. et al. , RF plasma method for production of single walled carbon nanotubes, U. S. Pat. Appl. Publ. US 2003 82,094 (Cl. 423 –447.3 ; D01F9/12), 1 may 2003, US appl. PV339,078.

[77] Cota – Sanchez G. , Synthèse de nanostructures de carbone en utilisant un réacteur plasma d’induction à haute fréquence, Thèse de doctorat, 2003, Université de Sherbrooke, Québec, Canada.

[78] Kato T. , Jeong G. H. , Hirata T. , Hatakeyama R. , Structure Control of carbon nanotubes using radio-frequency plasma enhanced chemical vapor deposition, Thin Solid Films, 2004, 457, 2-6.

[79] Boskovic B. O. , Stolojan V. , Khan R. A. , Haq S. , Silva S. R. P. , Large area synthesis of carbon nanofibres at room temperature, Nature materials, 2002, 1, 165-168.

[80] Wang X. , Hu Z. , Wu Q. , Chen Y. , Low-temperature catalytic growth of carbon nanotubes under microwave plasma assistance, Catalysis Today, 2002, 72, 205 – 211.

[81] Teo K. B. K. , Hash D. B., Lacerda, R. G. , Rupesinghe N. L. , Bell M. S. , Dalal S. H. , Bose D. , Govindan T. R. , Cruden, B. A. , Chhowalla M. , Amaratunga G. A. J. , Meyyappan M. , Milne W. , The significance of plasma heating in carbon nanotube and nanofiber growth, Nano Letters, 2004, 4 (5), 921–926.

[82] Li M. W. , Hu Z. , Wang X. Z. , Wu Q. , Chen Y. , Tian Y. –L. , Low-temperature syntheis of carbon nanotubes using corona discharge plasma at atmospherique pressure, Diamond and Related Materials, 2004, 13, 111-115.

[83] Morjan R. E. , Kabir M. S. , Lee S. W. , Nerushev O. A. , Lundgren P. , Bengtsson S. , Park Y. W. , Campbell E. E. B. , Selective growth of individual multiwalled carbon nanotubes, Current Applied Physics, 2004, 4 (6), 591-594.

[84] Hofmann S. , Ducall C. , Robertson J. , Kleinsorge B. , Low-temperature growth of carbon nanotubes by plasma-enhanced chemical vapor deposition, Applied Physics Letters, 2003, 83 (1), 135-137.

[85] Chen Y. , Patel S. , Ye Y. , Shaw D. T. , Field emission from aligned high-density graphitic nanofibers, 1998, 73 (15), 2119 – 2121.

[86] Han J. H. , Yang W. S. , Yoo J. B. , Park C. Y. , Growth and emission characteristics of vertically well - aligned carbon nanotubes grown on glass substrate by hot filament plasma -enhanced chemical vapor deposition, Journal of applied physics, 2000, 88, 12, 7363 – 7365

[87] Täschner C. , Pacal F. , Leonhardt A. , Spatenka P. , Bartsch K. , Graff A. , Kaltofen R. , Synthesis of aligned carbon nanotubes by DC plasma – enhanced hot filament CVD, Surface and Coatings Technology, 2003, 174-175, 81-87.

[88] Wang B. B. , Lee S. , Xu X. Z. , Choi S. , Yan H. , Zhang B. , Hao W. , Effects of the pressure on growth of carbon nanotubes by plasma – enhanced hot filament CVD at low substrate temperature, Applied Surface Science, 2004, 236, 6-12.

[89] Qin L. C. , Zhou D. , Krauss A. R. , Gruen D.M. , Growing carbon nanotubes by microwave plasma - enhanced chemical vapor deposition , Applied Physics Letters, 1998, 72 (26), 3437-3439.

[90] Choi Y. C. , Shin Y. M. , Lee Y. H. , Lee B. S. , Park G. S. , Choi W. B. , Lee N. S. , Kim J. M. , Controlling the diameter, growth rate, and density of vertically aligned carbon nanotubes synthesized by microwave plasma – enhanced chemical vapor deposition, Applied Physics Letters, 2000, 76 (17), 2367-2369.

[91] Kato T. , Jeong G. H. , Hirata T. , Hatakeyama R. , Tohji K. , Motomiya K. , Single – walled carbon nanotubes produced by plasma – enhanced chemical vapor deposition, Chemical Physics Letters, 2003, 381, 422-426.

[92] Yudasaka M. , Yamada R. , Sensui N. , Wilkins T. , Ichihaschi T. , Iijima S. , Mechanism of the effect of NiCo, Ni and Co catalysts on the yield of SWNT formed by pulsed Nd:YAG laser ablation, The Journal of Physical Chemistry B, 1999, 103, 6224-6229.

[93] Gavillet J. , Etude par microscopie électronique en transmission de la nucléation et de la croissance des nanotubes de carbone mono-feuillets, thèse de doctorat, spécialité : science des matériaux, 2001, université de Pierre et Marie curie, Paris VI.

[94] Saito Y. , Mitsumasa O. , Tomita M. , Hayashi T. , Extrusion of SWNT via formation of small particles condensed near an arc evaporative source, Chemical Physics Letters, 1995, 236, 419-426.

[95] Kataura H. , Kumazawa Y. , Maniwa Y. , Ohtsuka Y. , Sen R. , Suzuki S. , Achiba Y. , Diameter control of single-walled carbon nanotubes, Carbon, 2000, 38, 1691-1697.

[96] Gavillet J. , Loiseau A. , Ducastelle F. , Thair S. , Bernier P. , Stéphan O. , Thibault J. , Charlier J. –C. , Microscopic mechanisms for the catalytic assisted growth of SWNT, Carbon, 2002, 40, 1649-1663.

[97] Loiseau A. , Gavillet J. , Ducastelle F. Thibault J. , Stéphan O. , Bernier P. , Thair S. , Nucleation and growth of SWNT : TEM studies of the role of the catalyst, Physique, Comptes Rendus Physique, 2003, 4 (9), 975-991.

[98] Gorbunov A. , Jost O. , Pompe W. , Graff A. , Solid-liquid-solid growth mechanism of singlewall carbon nanotubes, Carbon, 2002, 40, 113-118.

[99] Kanzow H. , Lenski C. , Ding A. , Single-wall carbon nanotube diameter distributions calculated from experimental parameters, Physical Review B, 2001, 63, 125402-1–125402-6.

[100] Kanzow H. , Ding A. , Formation mechanism of single-wall carbon nanotubes on liquid-metal particles, Physical Review B, 1999, 60 (15), 11180-11186.

[101] Liu BB., Wagberg T., Nyeanchi E. B., Makarova T. L. , Zhu X. –M. , Sundqvist B. , Synthesis and characterization of SWNT and nanoparticles produced with Ce or Eu catalysts, Molecular Materials, 2000, 13, 1-4, 75-80.

[102] Saito Y., Yoshikawa T., Okuda M., Fujimoto N. , Sumiyama K. , Suzuki K. , Kasuya A. , Nishina Y. , Carbon nanocapsules encaging metals and carbides, Journal of Physics and Chemistry of Solids, 1993, 54, 1849.

[103] Pinault M. , Mayne-L’Hermite M. , Reynaud C. , Pichot V. , Launois P. , Ballutaud D. , Growth of multiwalled carbon nanotubes during the initial stages of aerosol-assisted CCVD, Carbon, 2005, 2968-2976.

[104] Nasibulin A. G. , Moisala A. , Brown D.P. , Jiang H. , Kauppinen E. I. , A novel aerosol method for single walled carbon nanotube synthesis, Chemical Physics Letters, 2005, 402, 227-232.

[105] Glerup M. , Kanzow H. , Almairac R. , Synthesis of multi-walled carbon nanotubes and nanofibres using the aerosol method with metal-ions as the catalyst precursors, Chemical Physics Letters, 2003, 377, 293-298.

[106] Xiong Y. ; Xie Y., Xiong Y. , Xie Y. , Li X. , Li Z. , Production of novel amorphous carbon nanostructures from ferrocène in low-temperature solution, Carbon, 2004, 42, I. 8-9, 1447-1453.

[107] Hwa Kiang C., Goddard A. W., Beyers R. , Bethune D. S. , Carbon nanotubes with single-layer walls, Carbon, 1995, 33, 7, 903-914.

[108] Kiang C.H., Goddard W.A., Beyers R. , Salem J.R. , Bethune D.S., Catalytic effects of heavy metals on the growth of carbon nanotubes and nanoparticules, Journal of Physics and Chemistry of Solids, 1996, 57, 35-39.

[109] Bethune D.S., Carbon and metals : a path to SWNTs, Physica B : Condensed Matter, 2002, 323 (1-4), 90-96.

[110] Jourdain V., Synthèse de nanotubes de carbone monofeuillets par arc électrique : influence du catalyseur, DEA Matériaux, 2000, Université Montpellier II.

[111] Maser W. K. , Bernier P. , Lambert J. M. , Elaboration and characterization of various carbon nanostructures, Synthetic Metals, 1996, 81, 243-250.

[112] Tarasov B.T., Muradyan V. E. , Shul’ga Y. M. , Krinichnaya E. P. , Kuyunko N. S. , Efimov O. N. , Obraztsova E. D. , Schur D. V. , Maehlen J. P. , Yartys V. A. , Lai H.-J. , Synthesis of carbon nanostructures by arc evaporation of graphite rods with Co-Ni and YNi2 catalysts, Carbon, 2003, 41, 1357-1364.

[113] Nishide D., Kataura H., Suzuki S., High-yield production of SWNT in nitrogen gas, Chemical Physics Letters, 2003, 372, 45-50.

[114] Maser W.K., Munoz E., Martínez M. T. , Benito A. M. , de la Fuente G. F., Study of parameters important for the growth of single wall carbon nanotubes, Optical Materials, 2001, 17, 331-334.

[115] Zhang H., Wang D., Xue X., Chen B. , Peng S. , The effect of helium gas pressure on the formation and yield of nanotubes in arc discharge, Journal of Physics D : Applied Physics, 1997, 30, L1-L4.

[116] Puretzky A. A, Schittenhelm H. , Fan X. , Lance M. J. , Allard L. F. , Geohegan D. B. , Investigations of single wall carbon nanotube growth by time-restricted laser vaporisation, Physical Review B, 2002, 65, 245425-1 - 245425-9.

[117] Jost O. , Gorbunov A. A. , Moller J. , Pompe W. , Graff A. , Friedlein R. , Liu X. , Golden M. S. , Fink J. , Impact of catalyst coarsening on the formation of SWNTs, Chemical Physics Letters, 2001, 339, 297-304.

[118] Byszewski P.; Lange H.; Huczko A. , Behnke J. F. , Fullerene and nanotube synthesis. Plasma spectroscopy studies, Journal of Physics and Chemistry of Solids, 1997, 58 (11), 1679-1683.

[119] Cui S., Scharff P., Siegmund C., Schneider D. , Risch K. , Klotzer S. , Spiess L. , Romanus H. , Schawohl J. , Investigation on preparation of multi-walled carbon nanotubes by DC arc discharge under N2 atmosphere, Carbon, 2004, 42 (5-6), 451-455.

[120] Hata K. , Futaba D. N. , Mizuno K. , Namai T. , Yumura M. , Iijima S. , Water-assisted highly efficient synthesis of impurity-free single-walled carbon carbon nanotubes, science, 2004, 306, 1362-1364.

[121] Maruyama S. , Kojima R. , Miyauchi Y. , Chiashi S. , Kohno M. , Low-temperature synthesis of high-purity single-walled carbon nanotubes from alcohol, Chemical Physics Letters, 2002, 360, 229-234.

[122] Maruyama S. , Einarsson E. , Murakami Y. , Edamura T. , Growth process of vertically aligned single-walled carbon nanotubes, Chemical Physcis Letters, 2005, 403, 320-323.

[123] Jourdain V. , Kanzow H. , Castignolles M., Loiseau A. , Bernier P., Sequential catalytic growth of carbon nanotubes, chemical Physics Letters, 364 (1-2), 27-33.

[124] Alvarez L., Mécanismes de croissance et étude vibrationnelle par spectroscopie Raman des nanotubes de carbone produits par la méthode solaire, Thèse de doctorat, université de Montpellier II.

[125] Sen R., Ohtsuka Y. , Ishigaki T. , Kasuya D. , Suzuki S. , Kataura H. , Achiba Y. , Time period for the growth of SWNTs in the laser ablation process : evidence from gas dynamic studies and time resolved imaging, Chemical Physics Letters, 2000, 332, 467-473.

[126] Puretzky A. A, Geohegan D. B. , Schittenhelm H. , Fan X. , Guillorn M. A. , Time-resolved diagnostics of single wall carbon nanotube synthesis by laser vaporisation, Applied Surface Science, 2002, 197-198, 552-562.

[127] Méténier K., Bonnamy S., Béguin F. , Journet C. , Bernier P. , Lamy de La Chapelle M. , Chauvet O. , Lefrant S. , Coalescence of SWNT and formation of MWNT under high-temperature treatments, Carbon, 2002, 40, 1765-1773.

[128] Loiseau A, Synthesis and growth of C-SWNTs, Cours d’Aussois, 2003.

[1] Pointu A-M. , Perrin J. , Jolly J. , Plasmas froids de décharge, Techniques de l’ingénieur, D 2830.

[2] Gonzalez - Aguilar, J. , Etude théorique et expérimentale de plasma pour des applications industrielles : découpe par plasma, Thèse de doctorat, 1999, Université de Cantabrie, Département de physique appliquée, Espagne.

[3] Plasmas froids : Génération, caractérisation et technologies, Publication de l’université de Saint – Etienne, 2004.

[4] Rollier J. -D. , Fulcheri L. , Gonzalez-Aguilar J. , Electrical characterisation of a low current-high voltage compact arc plasma torch, Proceedings 17th International Symposium on Plasma Chemistry, ISPC 17, Toronto, Canada, 2005, 388-389.

[5] Rollier J.-D. , Gonzalez - Aguilar J. , Metmemeijer R. , Fulcheri L. , Darmon A. , Duval-Brunel E. , Plasma assisted fuel reforming for on-board hydrogen rich gas production, Proceedings of the 2nd European Hydrogen Energy Conference EHEC 2005, Zaragoza, Espagne, 2005, 79-81.

[6] Petitpas G. , Rollier J. -D. , Gonzalez - Aguilar J. , Fulcheri L. , Review : A comparative study of non-thermal plasma assisted reforming technologies, Article accepté à International Journal of Hydrogen Energy.

[7] Reece Roth J. , Industrial Plasma Engineering, volume 1 Principles, Institute of Physics Publishing Bristol and Philadelphia, 2001.

[8] Salanne J. -P. , Contrôle du point de fonctionnement des décharges électriques par l’intermédiaire de leur alimentation, thèse de doctorat , Spécialité : Génie électrique, 2005, Institut national polytechnique de Toulouse.

[9] Club E.D.F arc électrique, l’arc électrique et ses applications, tome 2, 1985, Edition CNRS.

[10] Paulmier T. , Fulcheri L. , Use of non-thermal plasma for hydrocarbon reforming, Chemical Enginneering Journal, 2005, 106, 59 – 71.

[11] Rapport interne LEEI, Salanne, J. –P. , Picquet H. , Rapport sur les essais effectués sur la nouvelle alimentation pour un réacteur chimique, 2003.

[12] Nasibulin A. G. , Moisala A. , Brown D. P. , Kauppinen E. I . , Carbon nanotubes and onions from carbon monoxide using Ni(acac)2 and Cu(acac)2 as catalyst precursors, Carbon, 2003, 41, 2711-2724.

[13] Moisala A. , Parametric study of single-walled carbon nanotube synthesis via aerosol method”, communication orale, NanoteC & GDR-E, 2004, Batz-sur-Mer, France.

[1] Segui Y. , Diélectriques, courants de conduction, Techniques de l’ingénieur, p. D2301-5.

[2] Richard F. , Cormier J. M. , Pellerin S. , Chapelle J. , Physical study of a gliding arc discharge, Journal of Applied Physics, 1996, 79 (5), 2245-2250.

[3] Salanne J. P. , Contrôle du point de fonctionnement des décharges électriques par l’intermédiaire de leur alimentation, thèse de doctorat , spécialité : Génie électrique, 2005, Institut national polytechnique de toulouse.

[4] Badie J. M. ; Bresson J. ; Daïf A. ; Granier B. ; Détermination acoustique de la transition à l’écoulement laminaire du gaz plasmagène d’une torche à plasma, Journal de Physique III, 1996, 6, 1423-1433.

[5] Fridman A. A. , Petrousov A. , Chapelle J. , Cormier J. –M. , Czenichowski A. , Lesueur H. , Stevefelt J. , Modèle physique de l’arc glissant, Journal de Physique III, 1994, 4, 1449 – 1465.

[1] Monthioux M. , Le carbone dans tous ses états, Structure, textures et comportement thermique des solides polyaromatiques, Edit Bernier P. et Lefrant S. , Gordon et Breach, 1997, 127-182.

[2] Oberlin, A. , Goma, J. , Rouzaud J. N. , Techniques d’étude des structures et textures (microtextures) des matériaux carbonés, Journal de chimie physique, 1984, 81, 701-710.

[3] Springer Handbook of Nanotechnology, Brushan Editor, 2004, Introduction to Carbon Nanotubes, p.45.

[4] Bourrat X. , Contribution à l’étude de la croissance du carbone en phase vapeur (Etude des noirs conducteurs par microscopie électronique, RPE et modélisation fractale), Thèse de doctorat, Spécialité : sciences physiques, 1987.

[5] Oberlin A. , Chemistry and physics of carbon, High-resolution TEM studies of carbonization and graphitisation, volume 22, Thrower P. A., Marcel Dekker. Inc. , 1989.

[6] Monthioux M. , Allouche H. , Jacobsen R. L. , Chemical Vapor deposition of pyrolytic carbon on carbon nanotubes. Part 3 : Growth mechanisms, Carbon, 2006, 44, 3183-3194.

[7] Loiseau A. , Synthesis ans growth of C-SWNT, Cours d’Aussois, 2003.

[8] Oberlin A. , Carbonization and graphitization, Carbon, 1984, 22, 6, 521-541.

[9] De Fonton S. , Oberlin A. , Inagaki M. , Characterization by electron microscopy of carbon phases (intermediate turbostratic phase and graphite) in hard carbons when heat-treated under pressure, Journal of materials science, 1980, 15, 909-917.

[10] Saito Y. , Nanoparticules and filled nanocapsules, Carbon, 1995, 33 (7), 979-988.

[11] Baker R. T. K. , Harris P. S. , Chemistry and physics of carbon, The formation of filamentous carbon, 1978, 14.

[12] Ullmann’s Encyclopedia of Industrial Chemistry, Carbon, 2002.

[13] Donnet J. – B. , Voet A. , Carbon Black, Physics, Chemistry and Elastomer Reinforcement, Marcel Dekker Inc. , New York and Basel, 1976.

[14] Schwob Y. , Chemistry and physics of carbon, Acetylene black, Marcel Dekker, Inc. , NewYork, 1979, p.162.

[15] Kim K. S. ; Seo J. H. ; Nam J. S. ; Ju W. T. ; Hong S. H. ; Production of hydrogen and carbon black by methane decomposition using DC-RF Hydrid Thermal Plasmas, IEEE transactions on plasma science, 33, 2, 2005, 813-823.

[16] Kim K. S. , Lee K. S. , Ju W. T; , Hong S. H. , Synthesis of nanostructured carboneous materials by thermal decomposition of methane using DC thermal plasmas, 17th International Symposium on Plasma chemistry, Toronto, Ontario, Canada, 2005.

[17] Zielinski T. , Kijenski J. , Plasma carbon black – the new active additive for plastics, Composites : Part A 36, 2005, 467-471.

[1] Kee R. J. , Rupley F. M. , Miller J. A.CHEMKIN-II: A FORTRAN chemical kinetics package for the analysis of gas phase chemical kinetics. Sandia Report SAND 89-8009, 1989.

[2] Fluent Inc. 2004, Version 6.2.16.

[3] Belinov M. S. , Naidis G. V. , Modeling of hydrogen-rich gas production by plasma reforming of hydrocarbon fuels, International Journal of Hydrogen Energy, 2006, 31, 769-774.

[4] Smith G. P. , Golden D. M. , Frenklach M. , Moriarty N. W. , Eiteneer B. , Goldenberg M. , Bowman C. T. , Hanson R. K. , Song S. , Gardiner Jr. W. C. , Lissianski V. V. , Qin Z. , http://www.me.berkeley.edu/gri_mech.

[5] Pateyron B. , Delluc G. , Calvé N. , T&Twinner, la chimie et les propriétés de transports en ligne, dans l’intervalle de 300K à 20000 K, Technologie en Mécanique, 2006, 6, 651-654.

[6] Richard F. , Cormier J. M. , Peelerin S. , Chapelle J. , Physical study of a gliding arc reactors, Journal of Applied Physics, 1996, 79, 5, 2245-2250.

[7] Loiseau A. , Synthesis and growth of C-SWNTs, Cours d’Aussois 2003.

[1] Cerr M. , Bertolé G. , Dubresson J. , Guillemin C. , Richard M. , Verwaerde R. , Analyse industrielle I, Instrumentation industrielle volume 3, Technique et Documentation, 1996.

[2] Gonzalez-Aguilar J. , Chromatographie en phase gazeuse, Rapport interne, septembre 2005.

[3] Shimadzu, GC data sheet, Shimadzu gas chromatograph, analysis of inert Inorganic Gases, CA180-917A-GC-No.1, p.7, Complete Separation of H2, O2, N2, CO, CO2, CH4, C2H4, C2H6 and C2H4 with Applied Flow System.

[4] Le Blanc, Cours de chromatographies, Maîtrise de Chimie, Université de Nice Sophia-Antipolis, 2000-2001.

[5] Lide D. R. , Handbook of Chemistry and Physics, Edition 2002 – 2003.

Table of content

INTRODUCTION GENERALE

CHAPITRE I – NANOPARTICULES DE CARBONE, ETAT DE L’ART

I. NOIRS DE CARBONE

I.1. Généralités

I.2. Procédés de fabrication des noirs de carbone

I.3. Mécanismes de formation des noirs de carbone

II. NANOTUBES DE CARBONE

II.1. Généralités

II.2. Procédés plasma pour la synthèse en phase gazeuse de nanotubes de carbone

II.3. Mécanismes de croissance des nanotubes de carbone dans les procédés à haute température

II.4. Corrélations entre les conditions opératoires et les caractéristiques structurales des nanotubes monoparois

III. CONCLUSION

IV. REFERENCES

CHAPITRE II – DESCRIPTION DU DISPOSITIF EXPERIMENTAL POUR LA SYNTHESE DE NANOPARTICULES DE CARBONE

I. GENERALITES SUR LES PLASMAS

II. DEVELOPPEMENT D’UNE TORCHE PLASMA FONCTIONNANT A HAUTE TENSION ET FAIBLE COURANT COUPLEE A SON ALIMENTATION ELECTRIQUE

II.1. Principe de la torche plasma

II.2. Alimentation électrique

III. BANC EXPERIMENTAL

III.1. Schémas de principe et conception du dispositif expérimental

III.2. Réacteur plasma

III.3. Systèmes d’alimentation

III.4. Diagnostics

IV. CONCLUSION

V. REFERENCES

CHAPITRE III – RESULTATS EXPERIMENTAUX

I. CARACTERISATION DE LA TORCHE PLASMA SANS INJECTION DE REACTIF

I.1. Caractérisation électrique de la torche plasma

I.2. Caractérisation de la conversion par plasma de l’arcal 21

II. CARACTERISATION DU PROCEDE LORS DE L’INJECTION D’HYDROCARBURE

II.1. Problématique liée à l’injection d’hydrocarbure

II.2. Réaction de craquage de l’éthylène

II.3. Réaction de craquage de l’acétylène

III. CARACTERISATION DU PROCEDE LORS DE L’INJECTION D’HYDROCARBURE ET DE CATALYSEUR

III.1. Description des conditions opératoires

III.2. Influence des paramètres opératoires

III.3. Analyse qualitative des gaz de sortie du procédé par chromatographie en phase gazeuse

IV. CONCLUSION

V. REFERENCES

CHAPITRE IV – CARACTERISATIONS DES PRODUITS SYNTHETISES I. PRINCIPALES TECHNIQUES D’INVESTIGATIONS

I.1. Microscopie Electronique à Balayage, MEB

I.2. Diffraction des rayons X

I.3. Microscopie Electronique à Transmission, MET

II. TEXTURES A TENDANCE CONCENTRIQUE

II.1. Noirs de carbone « classiques »

II.2. Noirs de carbone de type noir d’acétylène

II.3. Coques de carbone remplies de métal

III. TEXTURES DE TYPE « PAPIERS FROISSES » ET « MICROPOREUX »

III.1. Textures de type « Papiers froissés »

III.2. Textures de type « microporeuses »

III.3. Textures» hétérogènes de type « papiers froissés » et « microporeux »

IV. TEXTURES FIBREUSES

IV.1. Nanotubes de carbone

IV.2. Nanofibres de carbone

V. AUTRES NANOTEXTURES CARBONEES OBTENUES

V.1. Tiges carbonées

V.3. Dépôts carbonés

VI. ANALYSES BET

VII. CORRELATIONS ENTRE LES CONDITIONS OPERATOIRES ET LES PROPRIETES TEXTURALES DES PRODUITS SYNTHETISES

VII.1. Influence de la nature du gaz plasmagène

VII.2. Influence du débit du gaz plasmagène

VII.3. Influence de la position d’injection de l’hydrocarbure

VIII. CONCLUSION

IX. REFERENCES

CHAPITRE V - CARACTERISATION GLOBALE DU REACTEUR

I. MODELISATION CINETIQUE CHIMIQUE DU REACTEUR

I.1. Hypothèses et approches générales

I.2. Résultats numériques

I.3. Conclusion

II. MODELISATION HYDRODYNAMIQUE DU REACTEUR

II.1. Hypothèses et approches générales

II.2. Résultats numériques

III. CONCLUSION

IV. REFERENCES

CONCLUSION ET PERSPECTIVES

ANNEXE : CHROMATOGRAPHIE EN PHASE GAZEUSE

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