Influence of lengths of millimeter-scale single-walled carbon nanotube on electrical and mechanical properties of buckypaper
© Sakurai et al.; licensee Springer. 2013
Received: 23 October 2013
Accepted: 16 December 2013
Published: 27 December 2013
The electrical conductivity and mechanical strength of carbon nanotube (CNT) buckypaper comprised of millimeter-scale long single-walled CNT (SWCNT) was markedly improved by the use of longer SWCNTs. A series of buckypapers, fabricated from SWCNT forests of varying heights (350, 700, 1,500 μm), showed that both the electrical conductivity (19 to 45 S/cm) and tensile strength (27 to 52 MPa) doubled. These improvements were due to improved transfer of electron and load through a reduced number of junctions for longer SWCNTs. Interestingly, no effects of forest height on the thermal diffusivity of SWCNT buckypapers were observed. Further, these findings provide evidence that the actual SWCNT length in forests is similar to the height.
The effective transfer of phonons, electrons, and load is known to increase with longer carbon nanotubes (CNTs) within CNT agglomerates. For example, in the percolation theory, electron transfer is expected to be achieved with a lesser number of CNTs by the use of longer CNTs in accordance with the relation Nc = 5.71 /Ls2, where Nc and Ls are percolation threshold and CNT length, respectively [1–4]. For example, higher electrical conductivity was observed for transparent conductive films using network thin films of longer CNTs [5, 6]. In addition, Miyata el al. reported a field effect transistor (FET) with high mobility using long single-walled CNTs (SWCNTs) . Further, in CNT/polymer composites, the beneficial effect of CNT length on the efficiency of phonon/electron transport and interfacial load transfer has been reported [8–11]. Such superiority in properties from long CNTs originates from the fewer CNT junctions, which interrupt phonon, electron, and load transfer, in a network structure of CNTs required to span the material.
Although these reports suggest the advantages of long CNTs on electron, thermal, and mechanical properties of a CNT assembly, this point has not been explicitly demonstrated experimentally. In other words, almost all the above experiments have employed only short CNTs, on the order of micrometers, with only one exceptional report by Zhu et al., who reported on the properties of composite of multiwalled CNTs with thick diameters (approximately 40 to 70 nm) and bismaleimide (BMI) . Particularly, there has been no report on the effect of length on the properties of SWCNTs exceeding 1 mm.
There are three reasons why research on the CNT length dependence of various properties of CNT assemblies has been difficult. First, the synthesis of long CNTs with uniform length in a large quantity is difficult. For example, Wang et al. reported the synthesis of long single-wall CNTs with a maximum length of 18.5 cm, but there were substantial variations in CNT length . Cao et al. reported an interesting approach for length-tunable CNT growth, but the length did not reach to millimeter scale . Furthermore, several groups reported the methods for classifying long/short CNTs, but this was not applied to CNTs that were longer than 10 μm in length [14–17]. Secondly, due to the tight entanglement among CNTs, the dispersion of CNTs without CNT scission is difficult. Ultrasonic agitation, which has been typically employed as a dispersion method, is known to shorten CNTs as it disentangles them . Finally, there is no available method to measure the lengths of individual CNTs longer than 100 μm. CNTs with lengths of several micrometers have been evaluated by atomic force microscopy (AFM) [8–11, 14–17], but this method encounters extreme difficultly when obtaining statistically significant data for long CNTs.
Using water-assisted chemical vapor deposition (CVD), we reported the synthesis of a vertically aligned SWCNT array (SWCNT forest) with height exceeding a millimeter . The SWCNT forests possessed several excellent structural properties, such as long length, high purity, and high specific surface area. This development opened up the potential for various new applications of CNTs, such as high-performance super-capacitors [20–23] and highly durable conductive rubbers [24, 25]. Subsequently, many groups reported the growth of long SWCNTs. For example, Zhong et al. reported the growth of SWCNT forests reaching 0.5 cm in length . Hasegawa et al. reported growth of SWCNT forests of several millimeters in length without an etching agent (water) . Numerous studies have also reported the synthesis of multiwalled CNT forests [28–30]. However, the following points remain unclear at present: the correlations between forest height and (1) the actual CNT length and (2) the electrical, thermal, and mechanical properties after formation of CNT assemblies.
In this research, we report the effect of the length of long CNTs on the electrical, thermal, and mechanical properties. Our results demonstrated a strong dependence of the SWCNT aggregate properties on the length. Specifically, buckypaper produced from 1,500 μm SWCNT forests exhibited approximately twice the electrical conductivity (52 vs. 27 S/m) and twice the tensile strength (45 vs. 19 MPa) of a buckypaper produced using 350 μm SWCNT forests. The use of an automated synthetic system equipped with height monitoring and dispersion strategy recently reported by Kobashi et al.  allowed overcoming the first two of the aforementioned issues, namely the required large quantity of long CNTs and CNT dispersion method to preserve length.
Fabrication of uniform buckypaper from SWCNTs of varying length
SWCNT forests of various lengths were synthesized in a fully automated CVD synthetic system equipped with a telecentric height measurement system using the water-assisted CVD process. A Fe/Al2O3 catalyst-sputtered silicon substrate was inserted into the 1-in. diameter quartz tube reactor (1 atm, 750°C). First, the substrate was exposed to a carrier gas (He, total flow of 1,000 sccm) containing hydrogen (40%) to form catalytic nanoparticles, and then SWCNTs were synthesized using a C2H4 (100 sccm) carbon feedstock and precisely regulated water vapor (100 to 150 ppm). The SWCNT forest height was controlled by using the height as feedback to the control software to automatically stop when the target height was achieved . In this way, SWCNT forests with precisely regulated heights (350, 700, 1,500 μm) could be synthesized in mass quantities. The uniformity of SWCNT forest heights was verified by scanning electron microscopy (SEM; Figure 1b,c,d) and digital photography (see Additional file 1: Figure S1).
Next, dispersions of the series of SWCNT forests of differing heights were prepared. Although conventional dispersion strategies aim to completely disentangle the CNTs into isolated particles, it also results in scission. Our strategy minimizes the scission by suspending the SWCNT agglomerates in a solvent while retaining the entanglement (Yoon et al.: Controlling the balance between exfoliation and damage during dispersion long SWCNTs for advanced composites, unpublished). We selected jet milling as the dispersion method because it has shown to preserve the SWCNT length with minimal scission, and it has also been shown that the resulting materials are suitable to fabricate SWCNT/polymer composite materials of high electrical conductivity (Yoon et al.: Controlling the balance between exfoliation and damage during dispersion long SWCNTs for advanced composites, unpublished) [24, 25, 33]. This benefit stems from a turbulent flow mechanism used in jet milling which exfoliates CNTs with minimal damage, in contrast to the cavitation mechanism used in conventional ultrasonic dispersion which is known to damage CNTs . Mixtures of SWCNT forest samples of specific length in methyl isobutyl ketone (MIBK) were introduced into a high-pressure jet-milling homogenizer (Nano Jet Pal, JN10, Jokoh), and suspensions (0.03 wt.%) were made by a high-pressure ejection through a nozzle (20 to 120 MPa, single pass).
The average thickness and mass densities of buckypapers prepared from SWCNT forest with different height
Height of SWCNT forest (μm)
Average thickness (μm)
Mass density (g/cm3)
Compressed at 20 MPa
Compressed at 100 MPa
Compressed at 20 MPa
Compressed at 100 MPa
Compressed at 20 MPa
Compressed at 100 MPa
Results and discussions
High electrical conductivity in buckypaper fabricated from high SWCNT forests
In order to verify that this apparent height-dependent variation in buckypaper conductivity was not due to differences in CNT quality, which has been shown to be essential for the various properties of buckypaper in previous works , Raman spectroscopy and electrical resistivity measurements of the as-grown SWCNT forests were carried out. The intensity ratios of the G-band (1,600/cm) and the D-band (1,350/cm) in the Raman spectra (see additional file 1: Figure S2), an indicator of CNT quality, were very similar (approximately 7). Peak positions and intensities in the radial breathing modes (RBM; 100 to 300/cm) were also nearly identical for all SWCNT forest heights. As the RBM peak position w (cm-1) is reported to be inversely proportional to the SWCNT diameter (nm), i.e., w = 248/d, these findings indicate that the effect of forest height on SWCNT diameter distribution was small. Furthermore, electrical conductivity of raw material forest was evaluated by applying a micro 4-probe onto the sides of SWCNT forests. Since the distances between the probes (50 μm) in a micro 4-probe was sufficiently short compared with the forest height, CNT length had almost no influence on the resistance values observed with this measurement. The measured resistance was nearly identical (206 to 220 Ω/sq) regardless of forest height (Figure 2b), indicating that quality of the SWCNTs did not degrade when growing forests of height to 1,500 μm, in accordance with the results of Raman spectroscopy.
As shown in the previous paragraph, taking into consideration the fact that forest height did not influence CNT quality, we conclude that the increase in buckypaper conductivity accompanying forest height was a result of the increased length of individual SWCNTs. In other words, improved electron transfer, thus higher conductivity, became possible from fewer junctions as a result of individual SWCNTs becoming longer. Furthermore, the 50% drop in buckypaper resistance by the approximately fourfold increase in SWCNT length (350 to 1,500 μm in forest height) indicate the strong effect of CNT-CNT junctions on the electrical resistance of SWCNT assemblies.
High tensile strength in buckypaper fabricated from high SWCNT forests
Relationship between forest height and SWCNT length
Additional insight can be garnered from the improvement in electrical and mechanical properties in tall forests on the actual length of the SWCNTs in a forest. Thus far, no direct evidence has been shown regarding this point. Our results indicate that the length of the SWCNTs within the forest is equal to the forest height.
Furthermore, we quantitatively discuss the effect of individual SWCNT length on electrical conductance and load transfer. Assuming that the electrical and mechanical properties are related to the number of junctions, the approximate double electrical conductivity and tensile strength exhibited by forests with heights of 1,500 μm compared with those of heights 350 μm indicates that half the number of SWCNT junctions are present for electron/load. We estimated that the SWCNTs from a 1,500-μm forest were, in fact, four times longer than those in a 350-μm forests by constructing a simple model describing the effective area of a SWCNT of a certain length as it spreads in a buckypaper. To make this model solvable, we assumed that the SWCNTs fell into a circular island with a uniform areal mass (i.e., SWCNT mass per unit area) within the buckypaper plane. The uniform areal mass assumption is justified by the overall macroscopic homogeneity of the buckypaper. With this consideration, the diameter of the effective area is proportional to the square root of the SWCNT length, and the effective area, where a SWCNT can make contact with another effective area, would be proportional to the length of the SWCNT. Therefore, we find that the four-time difference in forest height (1,500:350) matches well with the four-time difference in effective areas which would result in a twofold difference in junctions along a path and thusly explain the difference in electrical conductivity and mechanical strain. Importantly, we can also conclude that the length of a SWCNT within a forest, at least to a large extent, spans the height of the forest from the substrate to the forest top.
Relationship between buckypaper thermal conductivity and high SWCNT forest height
The present research shows that long SWCNTs with lengths exceeding the millimeter order greatly improved the electrical conductivity and mechanical strength of buckypaper. We attribute these improvements to electron and load transfer being improved through a reduced number of junctions due to increased CNT length. In addition, we conclude that the lengths of SWCNTs in forests that attain heights of 1,500 μm were close to that of the forest height. These findings indicate the need for taller SWCNT forests in the fabrication of buckypaper for high electrical conductivity and mechanical strength. Recently, Di et al. reported the ultrastrong and highly conducting CNT film by direct drawing from spinnable CNT array, where the tube length is around 220 μm . Our finding in this study suggest the possibility that the properties of CNT directly drawn from CNT forest can be further enhanced by using longer CNT array. In addition, we expect that using tall SWCNT forests would also raise the conductivity and mechanical strength of SWCNT networks in SWCNT/polymer composite materials.
Support by the New Energy and Industrial Technology Development Organization (NEDO) is acknowledged.
- Hu L, Hecht DS, Gruner G: Percolation in transparent and conducting carbon nanotube networks. Nano Lett 2004, 4: 2513–2517. 10.1021/nl048435yView ArticleGoogle Scholar
- Bekyarova E, Itkis ME, Cabrera N, Zhao B, Yu AP, Gao JB, Haddon RC: Electronic properties of single-walled carbon nanotube networks. J Am Chem Soc 2005, 127: 5990–5995. 10.1021/ja043153lView ArticleGoogle Scholar
- Unalan HE, Fanchini G, Kanwal A, Du Pasquier A, Chhowalla M: Design criteria for transparent single-wall carbon nanotube thin-film transistors. Nano Lett 2006, 6: 677–682. 10.1021/nl052406lView ArticleGoogle Scholar
- Simien D, Fagan JA, Luo W, Douglas JF, Migler K, Obrzut J: Influence of nanotube length on the optical and conductivity properties of thin single-wall carbon nanotube networks. ACS Nano 2008, 2: 1879–1884. 10.1021/nn800376xView ArticleGoogle Scholar
- Li ZR, Kandel HR, Dervishi E, Saini V, Xu Y, Biris AR, Lupu D, Salamo GJ, Biris AS: Comparative study on different carbon nanotube materials in terms of transparent conductive coatings. Langmuir 2008, 24: 2655–2662. 10.1021/la701880hView ArticleGoogle Scholar
- Gruner G: Carbon nanotube films for transparent and plastic electronics. J Mater Chem 2006, 16: 3533–3539. 10.1039/b603821mView ArticleGoogle Scholar
- Miyata Y, Shiozawa K, Asada Y, Ohno Y, Kitaura R, Mizutani T, Shinohara H: Length-sorted semiconducting carbon nanotubes for high-mobility thin film transistors. Nano Res 2011, 4: 963–970. 10.1007/s12274-011-0152-7View ArticleGoogle Scholar
- Wang X, Jiang Q, Xu W, Cai W, Inoue Y, Zhu Y: Effect of carbon nanotube length on thermal, electrical and mechanical properties of CNT/bismaleimide composites. Carbon 2013, 53: 145–152.View ArticleGoogle Scholar
- Frankland S, Caglar A, Brenner D, Griebel M: Molecular simulation of the influence of chemical cross-links on the shear strength of carbon nanotube-polymer interfaces. J Phys Chem B 2002, 106: 3046–3048. 10.1021/jp015591+View ArticleGoogle Scholar
- Mingo N, Broido D: Length dependence of carbon nanotube thermal conductivity and the “problem of long waves”. Nano Lett 2005, 5: 1221–1225. 10.1021/nl050714dView ArticleGoogle Scholar
- Coleman JN, Khan U, Blau WJ, Gun’ko YK: Small but strong: A review of the mechanical properties of carbon nanotube-polymer composites. Carbon 2006, 44: 1624–1652. 10.1016/j.carbon.2006.02.038View ArticleGoogle Scholar
- Wang X, Li Q, Xie J, Jin Z, Wang J, Li Y, Jiang K, Fan S: Fabrication of ultralong and electrically uniform single-walled carbon nanotubes on clean substrates. Nano Lett 2009, 9: 3137–3141. 10.1021/nl901260bView ArticleGoogle Scholar
- Cao A, Baskaran R, Frederick MJ, Turner K, Ajayan PM: Direction-selective and length-tunable in-plane growth of carbon nanotubes. Adv Mater 2003, 15: 1105–1109. 10.1002/adma.200304738View ArticleGoogle Scholar
- Ziegler KJ, Schmidt DJ, Rauwald U, Shah KN, Flor EL, Hauge RH, Smalley RE: Length-dependent extraction of single-walled carbon nanotubes. Nano Lett 2005, 5: 2355–2359. 10.1021/nl0510208View ArticleGoogle Scholar
- Ohmori S, Saito T, Shukla B: Fractionation of single wall carbon nanotubes by length using cross flow filtration method. ACS Nano 2010, 4: 3606–3610. 10.1021/nn100124vView ArticleGoogle Scholar
- Khripin C, Arnold-Medabalimi N, Zheng M: Molecular-crowding-induced clustering of DNA-wrapped carbon nanotubes for facile length fractionation. ACS Nano 2011, 5: 8258–8266. 10.1021/nn2029549View ArticleGoogle Scholar
- Khripin C, Tu X, Heddleston JM: High-resolution length fractionation of surfactant-dispersed carbon nanotubes. Anal Chem 2013, 85: 1382–1388. 10.1021/ac303349qView ArticleGoogle Scholar
- Lucas A, Zakri C, Maugey M, Pasquali M, van der Schoot P, Poulin P: Kinetics of nanotube and microfiber scission under sonication. J Phys Chem C 2009, 113: 20599–20605. 10.1021/jp906296yView ArticleGoogle Scholar
- Hata K, Futaba DN, Mizuno K, Namai T, Yumura M, Iijima S: Water-assisted highly efficient synthesis of impurity-free single-waited carbon nanotubes. Science 2004, 306: 1362–1365. 10.1126/science.1104962View ArticleGoogle Scholar
- Hiraoka T, Izadi-Najafabadi A, Yamada T, Futaba DN, Yasuda S, Tanaike O, Hatori H, Yumura M, Iijima S, Hata K: Compact and light supercapacitors from a surface-only solid by opened carbon nanotubes with 2200 m2/g. Adv Funct Mater 2010, 20: 422–428. 10.1002/adfm.200901927View ArticleGoogle Scholar
- Izadi-Najafabadi A, Yasuda S, Kobashi K, Yamada T, Futaba DN, Hatori H, Yumura M, Iijima S, Hata K: Extracting the full potential of single-walled carbon nanotubes as durable supercapacitor electrodes operable at 4 V with high power and energy density. Adv Mater 2010, 22: E235-E241. 10.1002/adma.200904349View ArticleGoogle Scholar
- Izadi-Najafabadi A, Futaba DN, Iijima S, Hata K: Ion diffusion and electrochemical capacitance in aligned and packed single-walled carbon nanotubes. J Am Chem Soc 2010, 132: 18017–18019. 10.1021/ja108766yView ArticleGoogle Scholar
- Izadi-Najafabadi A, Yamada T, Futaba DN, Yudasaka M, Takagi H, Hatori H, Iijima S, Hata K: High power supercapacitor electrodes from single-walled carbon nanohorn/nanotube composite. ACS Nano 2011, 5: 811–819. 10.1021/nn1017457View ArticleGoogle Scholar
- Sekitani T, Nakajima H, Maeda H, Fukushima T, Aida T, Hata K, Someya T: Stretchable active-matrix organic light-emitting diode display using printable elastic conductors. Nat Mater 2009, 8: 494–499. 10.1038/nmat2459View ArticleGoogle Scholar
- Ata S, Yumura M, Kobashi K, Hata K: Mechanically durable and highly conductive elastomeric composites from long single-walled carbon nanotubes mimicking the chain structure of polymers. Nano Lett 2012, 12: 2710–2716. 10.1021/nl204221yView ArticleGoogle Scholar
- Zhong G, Iwasaki T, Robertson J, Kawarada H: Growth kinetics of 0.5 cm vertically aligned single-walled carbon nanotubes. J Phys Chem B 2007, 111: 1907–1910. 10.1021/jp067776sView ArticleGoogle Scholar
- Hasegawa K, Noda S: Millimeter-tall single-walled carbon nanotubes rapidly grown with and without water. ACS Nano 2011, 5: 975–984. 10.1021/nn102380jView ArticleGoogle Scholar
- Hart AJ, Slocum AH: Rapid growth and flow-mediated nucleation of millimeter-scale aligned carbon nanotube structures from a thin-film catalyst. J Phys Chem B 2006, 110: 8250–8257. 10.1021/jp055498bView ArticleGoogle Scholar
- Eres G, Puretzky AA, Geohegan DB, Cui H: In situ control of the catalyst efficiency in chemical vapor deposition of vertically aligned carbon nanotubes on predeposited metal catalyst films. Appl Phys Lett 2004, 84: 1759–1761. 10.1063/1.1668325View ArticleGoogle Scholar
- Li Q, Zhang X, DePaula RF, Zheng L, Zhao Y, Stan L, Holesinger TG, Arendt PN, Peterson DE, Zhu YT: Sustained growth of ultralong carbon nanotube arrays for fiber spinning. Adv Mater 2006, 18: 3160–3163. 10.1002/adma.200601344View ArticleGoogle Scholar
- Kobashi K, Ata S, Yamada T, Futaba DN, Yumura M, Hata K: A dispersion strategy: dendritic carbon nanotube network dispersion for advanced composites. Chem Sci 2013, 4: 727–733. 10.1039/c2sc21266hView ArticleGoogle Scholar
- Yasuda S, Futaba DN, Yumura M, Iijima S, Hata K: Diagnostics and growth control of single-walled carbon nanotube forests using a telecentric optical system for in-situ height monitoring. Appl Phys Lett 2008, 93(143115):1–3.Google Scholar
- Aliev AE, Lima MH, Silverman EM, Baughman RH: Thermal conductivity of multi-walled carbon nanotube sheets: radiation losses and quenching of phonon modes. Nanotechnology 2010, 21(035709):1–11.Google Scholar
- Di J, Hu D, Chen H, Yong Z, Chen M, Feng Z, Zhu Y, Li Q: Ultrastrong, foldable, and highly conductive carbon nanotube film. ACS Nano 2012, 6: 5457–5464. 10.1021/nn301321jView ArticleGoogle Scholar
- Kataura H, Kumazawa Y, Maniwa Y, Umezu I, Suzuki S, Ohtsuka Y, Achiba Y: Optical properties of single-walled carbon nanotubes. Synt Metals 1999, 103: 2555–2558. 10.1016/S0379-6779(98)00278-1View ArticleGoogle Scholar
- Chen G, Futaba DN, Kimura H, Sakurai S, Yumura M, Hata K: Absence of an ideal single-walled carbon nanotube forest structure for thermal and electrical conductivities. ACS Nano DOI: 10.1021/nn404504f DOI: 10.1021/nn404504fGoogle Scholar
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