ACS Publications. Most Trusted. Most Cited. Most Read
Real-Time Imaging of Self-Organization and Mechanical Competition in Carbon Nanotube Forest Growth
My Activity
    Article

    Real-Time Imaging of Self-Organization and Mechanical Competition in Carbon Nanotube Forest Growth
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Mechanical Engineering and Laboratory for Manufacturing and Productivity, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States
    Department of Mechanical Engineering, University of Michigan, 2350 Hayward Street, Ann Arbor, Michigan 48109, United States
    § Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, California 94550, United States
    Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States
    School of Engineering, Indian Institute of Technology Mandi, Mandi, Himachal Pradesh 175001, India
    Department of Industrial Engineering, University of Pittsburgh, 3700 O’Hara Street, Pittsburgh, Pennsylvania 15261, United States
    *E-mail (A. John Hart): [email protected]
    Other Access OptionsSupporting Information (4)

    ACS Nano

    Cite this: ACS Nano 2016, 10, 12, 11496–11504
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.6b07251
    Published November 23, 2016
    Copyright © 2016 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The properties of carbon nanotube (CNT) networks and analogous materials comprising filamentary nanostructures are governed by the intrinsic filament properties and their hierarchical organization and interconnection. As a result, direct knowledge of the collective dynamics of CNT synthesis and self-organization is essential to engineering improved CNT materials for applications such as membranes and thermal interfaces. Here, we use real-time environmental transmission electron microscopy (E-TEM) to observe nucleation and self-organization of CNTs into vertically aligned forests. Upon introduction of the carbon source, we observe a large scatter in the onset of nucleation of individual CNTs and the ensuing growth rates. Experiments performed at different temperatures and catalyst particle densities show the critical role of CNT density on the dynamics of self-organization; low-density CNT nucleation results in the CNTs becoming pinned to the substrate and forming random networks, whereas higher density CNT nucleation results in self-organization of the CNTs into bundles that are oriented perpendicular to the substrate. We also find that mechanical coupling between growing CNTs alters their growth trajectory and shape, causing significant deformations, buckling, and defects in the CNT walls. Therefore, it appears that CNT–CNT coupling not only is critical for self-organization but also directly influences CNT quality and likely the resulting properties of the forest. Our findings show that control of the time-distributed kinetics of CNT nucleation and bundle formation are critical to manufacturing well-organized CNT assemblies and that E-TEM can be a powerful tool to investigate the mesoscale dynamics of CNT networks.

    Copyright © 2016 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.6b07251.

    • Histogram showing the size distribution of Fe particles and CNTs grown at 650 °C; in situ TEM images showing cap formation on the catalyst prior to CNT growth; scatter plots showing influence of catalyst size on CNT nucleation time and growth rate; in situ TEM observation of CNT growth capturing the incubation time and CNT catalyst size effect on CNT nucleation; in situ TEM observation of CNT mechanical interaction via swinging and random movement displacing one another during the growth prior to vertical alignment stage; estimation of the critical buckling force for a CNT; estimation of a lower bound of the kinking moment for a CNT; TEM observation of mechanical interactions for CNTs growing off the edges of holes in the thin TEM membranes (PDF)

    • In situ TEM video (accelerated 10×) of nucleation and self-organization of a high-density CNT network, forming a vertically aligned forest, at 650 °C (AVI)

    • In situ TEM visualization of low-density CNT growth leading to random network formation, observed at 750 °C (AVI)

    • In situ TEM video of CNT growth dynamics from an isolated catalyst particle, observed at 750 °C (AVI)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 36 publications.

    1. Tom A. J. Welling, Suzan E. Schoemaker, Krijn P. de Jong, Petra E. de Jongh. Carbon Nanofiber Growth Rates on NiCu Catalysts: Quantitative Coupling of Macroscopic and Nanoscale In Situ Studies. The Journal of Physical Chemistry C 2023, 127 (32) , 15766-15774. https://doi.org/10.1021/acs.jpcc.3c02657
    2. Zebin Liu, Jiangtao Wang, Ke Zhang, Xinyu Gao, Peng Liu, Qunqing Li, Lina Zhang, Shoushan Fan, Jing Kong, Kaili Jiang. Toward an Intelligent Synthesis: Monitoring and Intervening in the Catalytic Growth of Carbon Nanotubes. Journal of the American Chemical Society 2021, 143 (42) , 17607-17614. https://doi.org/10.1021/jacs.1c07598
    3. Jaegeun Lee, Golnaz Najaf Tomaraei, Moataz Abdulhafez, Mostafa Bedewy. Boosting Catalytic Lifetime in Chemical Vapor Deposition of Carbon Nanotubes by Rapid Thermal Pretreatment of Alumina-Supported Metal Nanocatalysts. Chemistry of Materials 2021, 33 (16) , 6277-6289. https://doi.org/10.1021/acs.chemmater.0c04692
    4. Lev Rovinsky, Barun Kumar Barick, Elnatan Lieberman, Efrat Shawat Avraham, Gilbert Daniel Nessim, Tamar Segal-Peretz, Noa Lachman. Alumina Thin-Film Deposition on Rough Topographies Comprising Vertically Aligned Carbon Nanotubes: Implications for Membranes, Sensors, and Electrodes. ACS Applied Nano Materials 2021, 4 (1) , 322-330. https://doi.org/10.1021/acsanm.0c02681
    5. Ahmed Aziz Ezzat, Mostafa Bedewy. Machine Learning for Revealing Spatial Dependence among Nanoparticles: Understanding Catalyst Film Dewetting via Gibbs Point Process Models. The Journal of Physical Chemistry C 2020, 124 (50) , 27479-27494. https://doi.org/10.1021/acs.jpcc.0c07765
    6. Jaegeun Lee, Moataz Abdulhafez, Mostafa Bedewy. Decoupling Catalyst Dewetting, Gas Decomposition, and Surface Reactions in Carbon Nanotube Forest Growth Reveals Dependence of Density on Nucleation Temperature. The Journal of Physical Chemistry C 2019, 123 (47) , 28726-28738. https://doi.org/10.1021/acs.jpcc.9b07894
    7. Jennifer Carpena-Núñez, Jorge Anibal Boscoboinik, Sammy Saber, Rahul Rao, Jian-Qiang Zhong, Matthew R. Maschmann, Piran R. Kidambi, Nicholas T. Dee, Dmitri N. Zakharov, A. John Hart, Eric A. Stach, Benji Maruyama. Isolating the Roles of Hydrogen Exposure and Trace Carbon Contamination on the Formation of Active Catalyst Populations for Carbon Nanotube Growth. ACS Nano 2019, 13 (8) , 8736-8748. https://doi.org/10.1021/acsnano.9b01382
    8. Nicholas T. Dee, Mostafa Bedewy, Abhinav Rao, Justin Beroz, Byeongdu Lee, Eric R. Meshot, Cécile A. C. Chazot, Piran R. Kidambi, Hangbo Zhao, Thomas Serbowicz, Kendall Teichert, Prashant K. Purohit, A. John Hart. In Situ Mechanochemical Modulation of Carbon Nanotube Forest Growth. Chemistry of Materials 2019, 31 (2) , 407-418. https://doi.org/10.1021/acs.chemmater.8b03627
    9. Rahul Rao, Cary L. Pint, Ahmad E. Islam, Robert S. Weatherup, Stephan Hofmann, Eric R. Meshot, Fanqi Wu, Chongwu Zhou, Nicholas Dee, Placidus B. Amama, Jennifer Carpena-Nuñez, Wenbo Shi, Desiree L. Plata, Evgeni S. Penev, Boris I. Yakobson, Perla B. Balbuena, Christophe Bichara, Don N. Futaba, Suguru Noda, Homin Shin, Keun Su Kim, Benoit Simard, Francesca Mirri, Matteo Pasquali, Francesco Fornasiero, Esko I. Kauppinen, Michael Arnold, Baratunde A. Cola, Pavel Nikolaev, Sivaram Arepalli, Hui-Ming Cheng, Dmitri N. Zakharov, Eric A. Stach, Jin Zhang, Fei Wei, Mauricio Terrones, David B. Geohegan, Benji Maruyama, Shigeo Maruyama, Yan Li, W. Wade Adams, A. John Hart. Carbon Nanotubes and Related Nanomaterials: Critical Advances and Challenges for Synthesis toward Mainstream Commercial Applications. ACS Nano 2018, 12 (12) , 11756-11784. https://doi.org/10.1021/acsnano.8b06511
    10. Eric R. Meshot, Darwin W. Zwissler, Ngoc Bui, Tevye R. Kuykendall, Cheng Wang, Alexander Hexemer, Kuang Jen J. Wu, and Francesco Fornasiero . Quantifying the Hierarchical Order in Self-Aligned Carbon Nanotubes from Atomic to Micrometer Scale. ACS Nano 2017, 11 (6) , 5405-5416. https://doi.org/10.1021/acsnano.6b08042
    11. Daria I. Tishkevich, Alla I. Vorobjova, Elena A. Outkina, Ihar U. Razanau, Tatiana I. Zubar, Anastasia A. Rotkovich, Anastasia A. Bondaruk, M. I. Sayyed, Sergei V. Trukhanov, M. V. Silibin, A. Yu. Gerasimenko, Valery M. Fedosyuk, Alex V. Trukhanov. Fabrication of high-density vertical CNT arrays using thin porous alumina template for biosensing applications. RSC Advances 2025, 15 (2) , 1375-1390. https://doi.org/10.1039/D4RA06442A
    12. Lili Zhang, Dai‐Ming Tang, Chang Liu. Growth Mechanism of Carbon Nanotubes Revealed by in situ Transmission Electron Microscopy. Small 2024, 20 (50) https://doi.org/10.1002/smll.202405736
    13. Ramakrishna Surya, Gordon L. Koerner, Taher Hajilounezhad, Kaveh Safavigerdini, Martin Spies, Prasad Calyam, Filiz Bunyak, Kannappan Palaniappan, Matthew R. Maschmann. CNT forest self-assembly insights from in-situ ESEM synthesis. Carbon 2024, 229 , 119439. https://doi.org/10.1016/j.carbon.2024.119439
    14. Kai Zhang, Kebei Chen, Jiangtao Di, Wenbin Gong, Zhuo Li, Jin Zhang, Yagang Yao. Construction of Medusa‐Like Adhesive Carbon Nanotube Array Induced by Deformation of Alumina Sheets. Small 2024, 20 (18) https://doi.org/10.1002/smll.202306722
    15. Golnaz Tomaraei, Moataz Abdulhafez, Mostafa Bedewy. Order-of-Magnitude Increase in Carbon Nanotube Yield Based on Modeling Transient Diffusion and Outgassing of Water From Reactor Walls. Journal of Manufacturing Science and Engineering 2024, 146 (4) https://doi.org/10.1115/1.4063965
    16. Kimberly A. Dick. Gas-phase materials synthesis in environmental transmission electron microscopy. MRS Bulletin 2023, 48 (8) , 833-841. https://doi.org/10.1557/s43577-023-00579-4
    17. Andres Eduardo Romero Valenzuela, Chayanaphat Chokradjaroen, Pongpol Choeichom, Xiaoyang Wang, Kyusung Kim, Nagahiro Saito. Carbon Fibers Prepared via Solution Plasma-Generated Seeds. Materials 2023, 16 (3) , 906. https://doi.org/10.3390/ma16030906
    18. Stephanie R. Morco, Brian D. Jensen, Anton E. Bowden. Curvature-induced defects on carbon-infiltrated carbon nanotube forests. RSC Advances 2022, 12 (4) , 2115-2122. https://doi.org/10.1039/D1RA07243A
    19. Lars I. van der Wal, Savannah J. Turner, Jovana Zečević. Developments and advances in in situ transmission electron microscopy for catalysis research. Catalysis Science & Technology 2021, 11 (11) , 3634-3658. https://doi.org/10.1039/D1CY00258A
    20. Kai Zhang, Wenbin Gong, Zhuo Li, Weigao Xu, Yagang Yao. Horizontally aligned surface segments enhancing the adhesion of carbon nanotube forests. Carbon 2021, 176 , 540-547. https://doi.org/10.1016/j.carbon.2021.02.002
    21. Golnaz Tomaraei, Jaegeun Lee, Moataz Abdulhafez, Mostafa Bedewy. Reducing Variability in Chemical Vapor Deposition of Carbon Nanotubes Based on Gas Purification and Sample Support Redesign. Journal of Micro and Nano-Manufacturing 2021, 9 (1) https://doi.org/10.1115/1.4050010
    22. Ashley L. Kaiser, Dale L. Lidston, Sophie C. Peterson, Luiz H. Acauan, Stephen A. Steiner, Roberto Guzman de Villoria, Amy R. Vanderhout, Itai Y. Stein, Brian L. Wardle. Substrate adhesion evolves non-monotonically with processing time in millimeter-scale aligned carbon nanotube arrays. Nanoscale 2021, 13 (1) , 261-271. https://doi.org/10.1039/D0NR05469K
    23. Divya Verma, Piyush Avasthi, Viswanath Balakrishnan. Upscaling mechanical properties of Al2O3 coated VACNT forest architecture under compression. Materials Characterization 2020, 170 , 110687. https://doi.org/10.1016/j.matchar.2020.110687
    24. Zichao Ma, Shaolin Zhou, Changjian Zhou, Ying Xiao, Suwen Li, Mansun Chan. Synthesis of Vertical Carbon Nanotube Interconnect Structures Using CMOS-Compatible Catalysts. Nanomaterials 2020, 10 (10) , 1918. https://doi.org/10.3390/nano10101918
    25. Guangfeng Hou, Mark J. Schulz. Carbon nanotube fibers spun directly from furnace. 2020, 37-59. https://doi.org/10.1016/B978-0-08-102722-6.00003-1
    26. Ayan Dey, Suranjana Mandal, Subhendu Bhandari, Chandrika Pal, Jonathan Tersur Orasugh, Dipankar Chattopadhyay. Characterization methods. 2020, 7-67. https://doi.org/10.1016/B978-0-12-819904-6.00002-5
    27. Taher Hajilounezhad, Damola M. Ajiboye, Matthew R. Maschmann. Evaluating the forces generated during carbon nanotube forest growth and self-assembly. Materialia 2019, 7 , 100371. https://doi.org/10.1016/j.mtla.2019.100371
    28. Jaegeun Lee, Moataz Abdulhafez, Mostafa Bedewy. Multizone Rapid Thermal Processing to Overcome Challenges in Carbon Nanotube Manufacturing by Chemical Vapor Deposition. Journal of Manufacturing Science and Engineering 2019, 141 (9) https://doi.org/10.1115/1.4044104
    29. Richard Li, Erica F. Antunes, Estelle Kalfon‐Cohen, Akira Kudo, Luiz Acauan, Wei‐Chang D. Yang, Canhui Wang, Kehang Cui, Andrew H. Liotta, Ananth Govind Rajan, Jules Gardener, David C. Bell, Michael S. Strano, J. Alexander Liddle, Renu Sharma, Brian L. Wardle. Low‐Temperature Growth of Carbon Nanotubes Catalyzed by Sodium‐Based Ingredients. Angewandte Chemie 2019, 131 (27) , 9302-9307. https://doi.org/10.1002/ange.201902516
    30. Richard Li, Erica F. Antunes, Estelle Kalfon‐Cohen, Akira Kudo, Luiz Acauan, Wei‐Chang D. Yang, Canhui Wang, Kehang Cui, Andrew H. Liotta, Ananth Govind Rajan, Jules Gardener, David C. Bell, Michael S. Strano, J. Alexander Liddle, Renu Sharma, Brian L. Wardle. Low‐Temperature Growth of Carbon Nanotubes Catalyzed by Sodium‐Based Ingredients. Angewandte Chemie International Edition 2019, 58 (27) , 9204-9209. https://doi.org/10.1002/anie.201902516
    31. Ashley L. Kaiser, Itai Y. Stein, Kehang Cui, Brian L. Wardle. Facile Patterning of Aligned Carbon Nanotube Architectures via Capillary-mediated Densification. 2019https://doi.org/10.2514/6.2019-1460
    32. Frances M. Ross, Andrew M. Minor. In Situ Transmission Electron Microscopy. 2019, 101-187. https://doi.org/10.1007/978-3-030-00069-1_3
    33. Mostafa Bedewy, Moataz Abdulhafez. Understanding Stochasticity in Carbon Nanotube Manufacturing. 2019, 31-64. https://doi.org/10.1016/B978-0-12-812667-7.00002-1
    34. Gyula Eres, C.M. Rouleau, A.A. Puretzky, D.B. Geohegan, H. Wang. Cooperative Behavior in the Evolution of Alignment and Structure in Vertically Aligned Carbon-Nanotube Arrays Grown using Chemical Vapor Deposition. Physical Review Applied 2018, 10 (2) https://doi.org/10.1103/PhysRevApplied.10.024010
    35. Ashley L. Kaiser, Itai Y. Stein, Kehang Cui, Brian L. Wardle. Process-morphology scaling relations quantify self-organization in capillary densified nanofiber arrays. Physical Chemistry Chemical Physics 2018, 20 (6) , 3876-3881. https://doi.org/10.1039/C7CP06869G
    36. M. Bahri, K. Dembélé, C. Sassoye, D. P. Debecker, S. Moldovan, A. S. Gay, Ch. Hirlimann, C. Sanchez, O. Ersen. In situ insight into the unconventional ruthenium catalyzed growth of carbon nanostructures. Nanoscale 2018, 10 (31) , 14957-14965. https://doi.org/10.1039/C8NR01227J

    ACS Nano

    Cite this: ACS Nano 2016, 10, 12, 11496–11504
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.6b07251
    Published November 23, 2016
    Copyright © 2016 American Chemical Society

    Article Views

    1642

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.