Thursday, February 2, 2023

Creating arbitrarily long graphene and carbon nanotubes. 2nd UPDATE: 2/24/2023: additional proposals for lengthened graphene-nanotube hybrids.

 Copyright 2023 Robert Clark

(patents pending)

(Appended at the bottom below are additional suggestions for combining graphene/carbon nanotubes.)

 Carbon nanotubes were created in the early 1990's. Experiments on them revealed extraordinary strength in the range of 1,000 times higher tensile strength per weight than standard grade steel plate and 100 times higher tensile strength per weight than the strongest steel wires available

 Graphene which can be regarded as carbon nanotubes flattened out were discovered about a decade later. Experiments confirmed they had comparable strength to carbon nanotubes.

 The only problem towards making them common industrial materials is that they have only been available in small sizes, at microns to a few millimeters in size.

 This is a proposal for constructing larger size graphene and carbon nanotubes. 

I.)Creating Large Graphene Sheets.

Recent research has produced hybrids of graphene and carbon nanotubes:

James’ bond: A graphene/nanotube hybrid

Rice University’s James Tour Group creates single-surface material for energy storage, electronics


Seven-atom rings (in red) at the transition from graphene to nanotube make this new hybrid material a seamless conductor. The hybrid may be the best electrode interface material possible for many energy storage and electronics applications. Image by Yang Yang/Yakobson Group


Nanotubes are grown from graphene to create nanoscale odako, so named for the giant Japanese kites they resemble. Image courtesy of the Tour Group

 The researchers were able to attach carbon nanotubes to graphene sheets. 


Several teams have been able to create such hybrids, [1], [2], [3], [4], [5]. Usually, these are formed by placing nanotubes onto graphene. However, one team was able to place graphene onto nanotube surfaces, [6].

 Repeating such hybrids into multiple layers, the strength and electrical properties of graphene and carbon nanotubes can be extended into 3-dimensions, [7], [8], [9], [10]:

Hybrid Structures of Graphene and Nanotubes Exhibit Unique Mechanical Properties

Carbon nanotube pillars between sheets of graphene may create hybrid structures with a unique balance of strength, toughness and ductility throughout all three dimensions, according to Rice University scientists. Five, seven or eight-atom rings at the junctions can force the graphene to wrinkle. Illustration by Shuo Zhao and Lei Tao

 However, other research had shown it is possible to "unzip" carbon nanotubes to turn them into graphene sheets:

Unzipping Carbon Nanotubes: A Peeling Method for the Formation of Graphene Nanoribbons

First published: 19 August 2009
 Graphical Abstract

Zipper examined: Elegant unzipping procedures result in the clean opening of multiwalled carbon nanotubes, leading to graphene nanoribbons (see scheme). Since graphene exhibits outstanding electronic properties, this method may be important in the development of modern nanoelectronic applications.

Description unavailable

 Several different methods have been found for accomplishing the unzipping, [11], [12], [13]. However, for my purposes the unzipping has to be targeted, as well as being able to cut the graphene at a targeted location in the graphene/nanotube hybrid. I therefore suggest using electron beams or x-ray beams to cut the graphene/carbon nanotubes at the specified locations:

 The idea would be to slice the graphene-nanotube along the lines shown then open up the material flat, to get a larger single sheet of graphene. Then the process would be repeated to attach further nanotubes, slice them open as well and open them up to get a larger sheet of graphene to make a graphene sheet arbitrarily large.

II.)Creating long nanotubes.

That's for creating arbitrarily large graphene. How about for arbitrarily long nanotubes? First the large graphene sheets would be created. Then methods for rolling up the graphene into carbon nanotubes would be used. Theoretical simulations had shown this possible, [14]:

Graphene Nanoribbons Zip Up
February 23, 2012• Physics 5, s29
Nanoscale planar materials such as graphene could be twisted to fabricate tubular objects.
O. Kit, Phys. Rev. B (2012)

Figure caption
O. Kit, Phys. Rev. B (2012)

   And this has been experimentally confirmed:

 2013 Oct 4; 4: 2548.
Published online 2013 Oct 4. doi: 10.1038/ncomms3548
Growth of carbon nanotubes via twisted graphene nanoribbons


1.)Graphene as an atomically thin interface for growth of vertically aligned carbon nanotubes.
Rahul Rao, Gugang Chen, Leela Mohana Reddy Arava, Kaushik Kalaga, Masahiro Ishigami, Tony F. Heinz, Pulickel M. Ajayan & Avetik R. Harutyunyan 
Scientific Reports volume 3, Article number: 1891 (2013)

2.)Growing Carbon Nanotubes from Both Sides of Graphene.
Jinlong Jiang*‡§, Yilun Li‡, Caitian Gao‡#, Nam Dong Kim‡, Xiujun Fan‡, Gunuk Wang‡, Zhiwei Peng‡, Robert H. Hauge‡⊥, and James M. Tour*‡⊥||
ACS Appl. Mater. Interfaces 2016, 8, 11, 7356–7362
Publication Date:February 23, 2016

3.)A Three-Dimensional Carbon Nanotube/Graphene Sandwich and Its Application as Electrode in Supercapacitors.
Zhuangjun Fan, Jun Yan, Linjie Zhi, Qiang Zhang, Tong Wei, Jing Feng, Milin Zhang, Weizhong Qian, Fei Wei
First published: 20 August 2010

Open Access
Published: 11 March 2019
High-Electrical-Conductivity Multilayer Graphene Formed by Layer Exchange with Controlled Thickness and Interlayer.
Hiromasa Murata, Yoshiki Nakajima, Noriyuki Saitoh, Noriko Yoshizawa, Takashi Suemasu & Kaoru Toko 
Scientific Reports volume 9, Article number: 4068 (2019)
5.)A seamless three-dimensional carbon nanotube graphene hybrid material
Yu Zhu, Lei Li, Chenguang Zhang, Gilberto Casillas, Zhengzong Sun, Zheng Yan, Gedeng Ruan, Zhiwei Peng, Abdul-Rahman O. Raji, Carter Kittrell, Robert H. Hauge & James M. Tour 
Nature Communications volume 3, Article number: 1225 (2012)

6.)Open Access
Published: 05 August 2013
Self-Assembly of Graphene on Carbon Nanotube Surfaces.
Kaiyuan Li, Gyula Eres, Jane Howe, Yen-Jun Chuang, Xufan Li, Zhanjun Gu, Litong Zhang, Sishen Xie & Zhengwei Pan 
Scientific Reports volume 3, Article number: 2353 (2013)

7.)AUGUST 2, 2018
Nanotube 'rebar' makes graphene twice as tough
by Mike Williams, Rice University
8.)Rebar Graphene
Zheng Yan†, Zhiwei Peng†, Gilberto Casillas∥, Jian Lin‡§, Changsheng Xiang†, Haiqing Zhou†, Yang Yang†‡, Gedeng Ruan†, Abdul-Rahman O. Raji†, Errol L. G. Samuel†, Robert H. Hauge†‡⊥, Miguel Jose Yacaman∥, and James M. Tour†‡§*
ACS Nano 2014, 8, 5, 5061–5068
Publication Date:April 2, 2014

9.)Pillared graphene gains strength

10.)Graphene and Carbon Nanotubes: Two Great Materials Even Better Together Researchers use carbon nanotubes to create a reinforced version of graphene.
09 APR 2014

11.)Published: 24 April 2009
Graphene nanoribbons
Unzipping nanotubes
Gavin Armstrong 
Nature Chemistry (2009)
Two methods for producing graphene nanoribbons by unzipping carbon nanotubes have been developed.

12.)Published: 16 April 2009
Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons
Dmitry V. Kosynkin, Amanda L. Higginbotham, Alexander Sinitskii, Jay R. Lomeda, Ayrat Dimiev, B. Katherine Price & James M. Tour 
Nature volume 458, pages872–876 (2009)

13.)Unzipping of Single-Walled Carbon Nanotube for the Development of Electrocatalytically Active Hybrid Catalyst of Graphitic Carbon and Pd Nanoparticles.
Siniya Mondal, Sourov Ghosh, and C. Retna Raj
ACS Omega 2018, 3, 1, 622–630
Publication Date:January 19, 2018

14.)Twisting graphene nanoribbons into carbon nanotubes
O. O. Kit, T. Tallinen, L. Mahadevan, J. Timonen, and P. Koskinen
Phys. Rev. B 85, 085428 – Published 23 February 2012

UPDATE: 2/14/2023: Squashed together carbon nanotubes and graphene sheets.

(patents pending)  
 A recent report demonstrated producing graphene sheets from squashing carbon nanotubes under diamond anvils:

New Research Narrows the Gap for Graphene Nanoribbon Applications
Cvetelin Vasilev, Ph.D.

Published: 06 September 2021
Sub-10-nm graphene nanoribbons with atomically smooth edges from squashed carbon nanotubes.
Changxin Chen, Yu Lin, Wu Zhou, Ming Gong, Zhuoyang He, Fangyuan Shi, Xinyue Li, Justin Zachary Wu, Kai Tak Lam, Jian Nong Wang, Fan Yang, Qiaoshi Zeng, Jing Guo, Wenpei Gao, Jian-Min Zuo, Jie Liu, Guosong Hong, Alexander L. Antaris, Meng-Chang Lin, Wendy L. Mao & Hongjie Dai 
Nature Electronics volume 4, pages 653–663 (2021) (behind paywall)
Free PDF: 


 Then the proposal is to use graphene sheets and/or carbon nanotubes laid one on top of another but with only for a short overlap distance compared to their lengths. The test is to see if the high pressure compression can induce the carbon-carbon bonds of graphene/nanotubes between the layers of the graphene/nanotubes. Previous work with graphene and nanotubes have been able to induce much weaker van der Waals bonds between the carbon atoms. These do not have the same strength as the carbon-carbon covalent bonds that prevail in graphene and carbon nanotubes.

 The purpose of the short overlap distance compared to their lengths is that likely there will be a combination of the stronger carbon-carbon bonds and van der Waals bonds between the layers. You might then need several layers to make the equivalent cross-sectional strength of a single graphene/nanotube layer. However, by making this portion of the composite small compared to the rest of the graphene/nanotubes the overall strength to weight ratio will be close to that of the pure graphene or carbon nanotubes.

2nd UPDATE, 2/24/2023: Cyclic graphene growing nanotubes growing graphene.

(patent pending)

 Above was first described methods of growing carbon nanotubes on graphene, as references, [1], [2], [3], [4], [5]. However, reference [6] described growing graphene on nanotubes:

Open Access
Published: 05 August 2013
Self-Assembly of Graphene on Carbon Nanotube Surfaces.
Kaiyuan Li, Gyula Eres, Jane Howe, Yen-Jun Chuang, Xufan Li, Zhanjun Gu, Litong Zhang, Sishen Xie & Zhengwei Pan 
Scientific Reports volume 3, Article number: 2353 (2013)

  Then the proposal is to cycle repetitively first of growing nanotubes onto graphene and then growing graphene onto nanotubes to produce arbitrarily large graphene-nanotube hybrids.


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