Carbon 42 (2004) 17831791 www.elsevier.

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Protocol for the characterization of single-wall carbon nanotube material quality

Sivaram Arepalli a, Pavel Nikolaev a,*, Olga Gorelik a, Victor G. Hadjiev b, Williams Holmes a, Bradley Files c, Leonard Yowell c
a

G.B.Tech Inc./NASA-Johnson Space Center, Mail code ES4-GBT, 2101 Nasa Road One, Houston, TX 77058, USA b Texas Center for Superconductivity and Advanced Materials, University of Houston, Houston, TX 77204, USA c NASA-Johnson Space Center, Mail code ES4, 2101 Nasa Road One, Houston, TX 77058, USA Received 8 April 2003; accepted 7 March 2004 Available online 30 April 2004

Abstract Single wall carbon nanotubes (SWCNTs) can be synthesized and puried by a number of techniques, and always contain certain amount of impurities of varying composition (mostly metal catalyst and non-tubular carbon), as well as defects resulting from purication. Particular purication route also aects homogeneity of nanotube material and its dispersability in organic solvents, which are important in the subsequent application development. A number of analytical characterization tools have been used successfully in the past years to access various properties of nanotube materials, but lack of standards makes it dicult to compare these measurements across the board. In this work we report on the protocol which standardizes measurements in TEM, SEM, TGA, Raman and UVVIS spectrometer, consumes <30 mg of material, and was found to provide fast and reliable feedback in the development of purication techniques. The amount of residual metal catalyst is determined directly, and numerical measures are established for parameters such as homogeneity, thermal stability and dispersability, to allow easy comparison of SWCNT materials. Quantitative measurement of non-tubular carbon impurities still remains a problem, and we have to rely on qualitative electron microscopy observations. 2004 Elsevier Ltd. All rights reserved.
Keywords: A. Carbon nanotubes; C. Thermal analysis, electron microscopy; Raman spectroscopy; D. Defects

1. Introduction Single wall carbon nanotubes (SWCNTs) form a new class of materials that has attracted large interest in the scientic community because of their extraordinary properties [13]. These nanotubes can be produced by a variety of techniques including carbon arc, laser ablation, chemical vapor deposition and carbon monoxide disproportionation [47]. The as-produced material is known to be inhomogeneous and contain a variety of impurities including carbon-coated metal clusters, amorphous carbon, and other carbon compounds including fullerenes. The type and extent of these impurities change with the production method used. The

Corresponding author. Tel.: +1-281-483-5946; fax: +1-281-2445918. E-mail address: pasha.nikolaev1@jsc.nasa.gov (P. Nikolaev). 0008-6223/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2004.03.038

production process also inuences the length, diameter, chirality and surface moiety of the nanotubes (and nanotube bundles). It is indeed a challenge to determine all these impurity levels and characterize this material to a reasonable extent without incurring too much time and expenditure. During the last few years, several researchers developed purication procedures to increase the percentage of SWCNTs and used a variety of analytical techniques to characterize the puried material [813]. Dierent purication steps are used depending on the source of the starting material and on the extent of purication needed. The purication procedures include boiling in hot water, slow oxidation in air, hot acid digestion, extensive ultra-sonication, centrifugation, annealing, etc. While removing the impurities, the purication processes seem to damage some of the SWCNTs and also modify the nanotube surfaces by the addition of functional groups. It is noted that the dispersability

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(into solutions) of the puried material changes drastically with purication steps. For example, the highly crystalline pure nanotube material obtained after a high temperature annealing is found to be very dicult to disperse. This crystalline material therefore is not suitable for preparing nano-composites. It is also to be noted that the SWCNTs are damaged from the severe ultra-sonication used to get the puried material into solution. The ease of getting the material into solution (solvability) and the extent of avoiding precipitation/agglomeration for long duration depend on the starting material as well as the purication steps. The most common analytical techniques used to characterize purity of nanotubes are transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetry (TGA) and Raman spectroscopy [813]. All of them have been adapted in the current work, with emphasis on standardizing measurements to facilitate easy comparison of results. There are few analytical approaches that can provide answers about dispersion of nanotubes in solvents. Long-term stability of nanotube suspensions is often used as a good indicator of the eectiveness of various organic solvents and/or surfactants [14], but does not distinguish suspensions of individual tubes vs. bundles. This approach is adapted with some improvement in the current work. Laser-induced uorescence (LIF) was recently observed in nanotubes suspended in D2 O in the presence of SDS (sodium dodecyl sulphate) [15]. Researchers have argued that LIF can only occur in semiconducting nanotubes individually suspended in water, therefore observation of LIF can be a proof that individual nanotubes are present in suspension. There are theoretical results [16] showing that Raman breathing mode (RBM) peaks of nanotubes in a bundle are upward shifted by 515% compared to that of individual nanotubes. But since there always is a certain distribution of nanotube diameters in a given sample, and any bundle can consist of nanotubes of varying diameters, it would be impossible to separate contributions from individual and bundled nanotubes. The shape of Gband peak in Raman spectra (appearance of wide Mband on the left shoulder of G-band) can also be indicative of the presence of bundled metallic tubes [17]. A very common option is AFM (atomic force microscopy) measurements of the bundle heights of nanotubes deposited onto suitable substrate from solution [18]. Smaller average bundle size is indicative of better dispersion. Unfortunately, bundle size can change as nanotubes are transferred onto substrate, therefore such measurements do not necessarily reect the state of dispersion in original solvent. Nanotube suspension can be ash-frozen as a thin layer and studied in cryogenic TEM [14]. This presumably maintains the state of nanotube dispersion in the original solution. Resolution

and stability issues in cryo-TEMs may prevent one from truly observing individual nanotubes this way. Optical microscopy was used to assess dispersion of nanotubes in polyimide lms [19], looking for presence and size of large nanotube agglomerates. Electrical conductivity and percolation threshold in such lms [19] can also serve as an indirect measure of nanotube dispersion. Presumably, at a given nanotube loading, better dispersion will decrease the percolation threshold. X-ray and neutron diraction patterns are sensitive to the average bundle size and diameter distribution of nanotubes [20]. Unfortunately, they are even more sensitive to the crystallinity of nanoropes and presence of intercalants. It is realized that the variability of the material from dierent sources and their modications with purication processes demand a close scrutiny while using them for applications. It is imperative to have a well characterized material in order to assess the variability of the additional steps used for trying new applications. For example, the preparation and evaluation of nano-composites require measurements that can follow the matrix before and after addition of SWCNT material. There is a strong need to use standard methods to characterize the SWCNT material to improve across the board comparison of dierent samples (both unpuried and puried). The present study is an attempt to develop protocols that can be used reliably within a short time to characterize the SWCNT material consistently. The protocol can be used for unpuried as well as puried carbon nanotube material and can be used for other nanomaterials with slight modications. It was rst mentioned in Ref. [2]. The NASA-JSC protocol for characterization of SWCNTs establishes numerical measures for homogeneity, dispersability, metal content and thermal stability so that comparison of various samples is simple. Nontubular carbon content is estimated qualitatively. Standard analytical techniques are summarized in Table 1 and include SEM, TEM, TGA, Raman and UVVIS spectrometry. Images from SEM are used to determine nature of the SWCNTs and a rough idea about material quality. Higher resolution images from TEM are used mostly to monitor the surface texture of individual ropes and qualitative determination of non-tubular carbon impurities. Raman spectra are used to estimate the extent of amorphous carbon as well as damage to the tubes. Analysis of TGA data is used to quantify the quality of tubes, as well as extent of non-carbon impurities in the collected sample [21]. Homogeneity of the sample is judged by standard deviations of the oxidation temperature and metal content obtained in three separate TGA runs. Absorption spectra of nanotube solutions are obtained in a UVVISNIR spectrometer and variation of optical density with time serves as a measure of dispersability of SWCNTs.

S. Arepalli et al. / Carbon 42 (2004) 17831791 Table 1 Parameter Purity Technique TGA SEM/TEM EDS Raman TGA TGA SEM/TEM Ultra-sonication UV/VIS/NIR Analysis

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Thermal stability Homogeneity

Dispersability

Quantitativeresidual mass after TGA in air at 5 C/min to 800 C Qualitativeamorphous carbon impurities Qualitativemetal content Qualitativerelative amount of carbon impurities and damage/disorder Quantitativeburning temperature in TGA in air at 5 C/min to 800 C, dM =dT peak maximum Quantitativestandard deviation of burning temperature and residual mass taken on 35 samples Qualitativeimage comparison Qualitativetime required to fully disperse (to the eye) low conc. SWCNT in DMF using standard settings Quantitativerelative change in absorption spectra of sonicated low concentration SWCNT/ DMF solution

2. Experimental details The details of the NASA-JSC protocol involve specifying the operating conditions for collecting characterization data from a variety of analytical techniques. The unpuried material can be used as is, but the puried material needs to be in the form of a bucky paper [13] for characterization tests. Goal is to have about 30 mg of dry puried material (bucky paper) for these tests.

2.4. Sample prepared for TEM The procedure is as follows: bath sonicate 0.1 mg of bucky paper in 20 ml of methanol for 10 min; place one drop of this suspension on the 200 mesh lacey carbon TEM grid placed on a tissue paper; dry the grid in an oven at 120 C for at least 2 h. 2.5. Sample analysis 2.5.1. Purity and metal content A quantitative measure of residual metal catalyst in nanotube sample is provided by measuring TGA residue, under assumption that upon heating to 800 C in air all carbon and metal are converted into corresponding oxides. Note that samples often contain traces of other elements (for example Si and Cl), which may introduce small error in the calculated metal content. We obtained TGA traces using three samples (3 mg each), with a heating rate of 5 C/min in air from room temperature to 800 C. (If specimen weight is still decreasing at 800 C, the nal temperature should be increased accordingly). The weight of ashes is measured independently on a microbalance afterwards to apply proper correction if necessary for the residue weight, since TGA baseline can deviate from zero at high temperature. The peak position of the mass derivative (dm=dT ) is recorded as an indicator of the oxidation temperature (see Section 2.5.3). The average values of the oxidation temperature To and residual mass Mr are recorded, as well as their standard deviations. For qualitative estimation, three EDS (energy dispersive spectroscopy) spectra of one sample (from three different-looking areas) associated with SEM images are recorded at 20 kV accelerating voltage, 3 mm spot size, 10 mm working distance, 2000 (2 k) magnication. The EDS data indicate the relative amounts of metals and other non-carbon elements in SWCNT material. Note that EDS is notoriously unreliable in determining carbon because of hydrocarbon contamination present

2.1. Samples The present study provides comparison of two samples. Both are HiPco batch 87, rst used as-is and second puried by soft-baking procedure [10], which includes slow oxidation in wet air at 250 C for 24 h followed by stirring in concentrated HCl and repeated washing with DI water. 2.2. Bucky paper preparation After last stage of purication (washing), samples are in a form of slurry. This water slurry is ltered, washed with deionized water one more time and then with methanol on the membrane lter. The material collected on the lter (bucky paper) is placed in a vacuum oven and dried at 120 C for two hours (or in a regular oven if vacuum oven is not available). This bucky paper is then stored in a closed container minimizing exposure to moisture in the air. 2.3. Sample prepared for SEM Very small piece of bucky paper is mounted on aluminum SEM holder puck using double-sided carbon tape. Unpuried material is mounted on the SEM holder using a tab of silver paint.

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in all SEMs and TEMs, and poor sensitivity of EDS detectors in the low-energy end of spectrum, where carbon peak is found. Higher spatial resolution EDS is recorded while obtaining TEM images with 40 k magnication at 160 kV operating voltage. We have found that TEMEDS is not nearly as useful as SEM EDS for a number of reasons. TEMEDS has strong Cu peaks from the stray signal originating with copper TEM grids (which can be ignored). It also has strong Si peak, since grids are usually contaminated with silicone vacuum grease during fabrication. This makes it impossible to monitor a small amount of silicon, which is actually present in nanotubes and presumably comes from the glassware used in nanotube purication. 2.5.2. SWCNT content and non-SWCNT carbon content The relative amounts of non-tubular carbon impurities and nanotubes in the sample are qualitatively estimated from SEM and TEM images. SEM images from three dierent looking areas from one sample are taken with 10 kV accelerating voltage, a spot size of 3, and a working distance of 4 mm. Each area is imaged with magnications 20 and 50 k for a total of six images. For TEM, a representative area is selected after surveying the TEM grid. Three images are recorded; two at 500 k and one at 200 k magnication with a 160 kV operating voltage. Raman scattering measurements are also used to corroborate SEM and TEM examination. Raman spectroscopy provides express, non-destructive, and preparation-free estimate of carbon content. Practically all carbon allotropes are Raman active. These include fullerenes, carbon nanotubes, amorphous carbon (both sp2 (a-C) and sp3 (ta-C)), partial amorphous and crystalline carbon (glassy carbon, diamond like carbon), micro-, nano- or poly-crystalline carbon (diamond, hard carbon, graphite), crystalline carbon (diamond and graphite). Fullerenes, carbon nanotubes and crystalline carbon feature sharp Raman lines that make them clearly distinguishable from the other carbon allotropes [22]. All carbon forms contribute to the Raman spectra in the range 10001700 cm1 typically giving rise to a two-band feature with peaks at 1300 cm1 (D-band) and 1600 cm1 (G-band). The position, width and relative intensity of the peaks vary with carbon allotropes [23] and can be used, with some limitations, for identication of non-SWCNT content. D-band usually creates ambiguities whether to be assigned to nonSWCNT carbon or to defects on SWCNTs. The protocol procedure suggests recording spectra from three dierent-looking areas on one sample under a microscope with a 50 objective and using 780 nm laser excitation. The spectra are recorded within the range of 1003000 cm1 at spectral resolution better than 3 cm1 . The latter is sucient to resolve the sharpest Raman lines of SWCNTs [24].

Each Raman spectrum is collected three times and the representative spectrum is a median of the measured spectra instead of their average. This procedure allows elimination of spurious spikes in the Raman spectra and is also known as cosmic ray reduction. We use the following landmark carbon properties in analysis of the non-SWCNT content excited at 780 nm: (1) All forms of amorphous carbon give very broad, >100 cm1 (FWHM), D and G bands in contrast to crystalline (single crystal, micro-, nano-crystalline) carbon allotropes and SWCNTs; (2) D-band in SWCNTs is within the range 12851300 cm1 [25] having linewidth 1030 cm1 [23]; Crystalline graphite-like allotropes and glassy carbon D-band is found at 13051330 cm1 and linewitdths 3060 cm1 [26]; Multi-wall carbon nanotubes (MWCNT) exhibit D-bands with parameters close to those of the crystalline graphite-like allotropes [25]. We note that 780 nm laser excites only a part of the SWCNTs in carbon material. Also, at this excitation the C60 Ag (1) line at 495 cm1 is stronger than Ag (2) at 1468 cm1 [22]. The current protocol emphasizes on purity and homogeneity of carbon material and for this purpose one laser excitation is sucient. The low wavenumber region (100400 cm1 ) is indicative of the SWCNT content and is used to estimate the average diameter distribution of the SWCNTs. An extended protocol that includes determination of the SWCNTs diameter distribution would require recording of Raman spectra using multiple laser excitations. 2.5.3. Thermal stability Oxidation temperature To of the sample in TGA (as mentioned in 2.5.1) can serve as a measure of thermal stability of nanotubes in air. It depends on a number of parameters. For example, smaller diameter nanotubes are believed to oxidize at lower temperature due to higher curvature strain. Defects and derivatization moiety in nanotube walls can also lower the thermal stability. Active metal particles present in the nanotube samples catalyze carbon oxidation, so the amount of metal impurity in the sample can have a considerable inuence on the thermal stability. It is impossible to distinguish these contributions, but nevertheless thermal stability is a good measure of the overall quality of nanotube sample. Higher oxidation temperature is always associated with purer, less defective samples. Note that oxidation temperature can be dened alternatively as an onset (deection point) temperature, or as a maximum in the derivative weight curve, also known as DTG (derivative of thermogravimetry) curve. In case of nanotube samples, onset temperature is typically poorly dened, since transitions are rather broad, and initial mass loss is attributed to the oxidation of amorphous carbon impurities rather than nanotubes themselves. Maximum in the DTG curve, on the other hand, can be dened and measured precisely, and is associated with

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burning of nanotubes rather than impurities. Therefore, we dene To as a DTG maximum. In the course of experimental work we have noticed that oxidation temperature is dependent on the heating rate [21]. Higher heating rates can cause nanotube combustion [27], which leads to qualitatively dierent shape of TGA traces and larger standard deviations of Mr and To [21]. The 5 C/min heating rate was chosen taking into account these eects. It is important to emphasize that in order to be able to compare the To values across the board, all TGA measurements have to be performed at the same heating rate. 2.5.4. Homogeneity The extent of homogeneity can be estimated from any of the analytical techniques. The current protocol suggests using the three TGA runs to obtain oxidation temperature and residual mass. The standard deviations of oxidation temperature and residual mass serve as a numerical measure of homogeneity of the sample. It is to be noted that Raman data can also be used to assess the homogeneity of the sample by monitoring the D and G bands as discussed in Section 2.5.2. 2.5.5. Dispersability First, we need to dene what dispersion means. It is known that nanotubes can form relatively stable suspensions at high concentration in a number of solvents and surfactants, but nanotubes still exist as bundles of varying sizes, i.e. nanoropes form suspension in solvent, but individual nanotubes are not present. This can be dened as macro-dispersion of nanotubes. In contrast, nano-dispersion can be dened as further separation of nanotube bundles into individual nanotubes. It is to be noted that macro-dispersed material in most cases may not be nano-dispersed. The current study focuses on the macro-dispersion only. Determining the dispersability involves testing for two parameters: how easily nanotubes disperse in solvent, and how well they stay in suspension. The rst task is accomplished by dispersing nanotubes in DMF (dimethyl formamide, which seems to produce stable suspensions with little eort) in ultrasound bath. Time required to get rid of visible agglomerates serves as a numerical measure of nanotubes ability to disperse. The second task is accomplished by monitoring the change in optical density of the resulting suspension with time. Upon removal from the ultrasound bath, nanotubes gradually occulate from suspension and sink to the bottom of the cuvette (sometimes nanotubes actually oat to the top of the cuvette). This causes slow decrease in the optical density of suspension, which provides numerical measure of nanotubes ability to stay in suspension.

The procedure is as follows: Bath sonicate three separate samples, 0.1 mg in 10 ml DMF each, (in 25 ml tall test tube); sonicator conditions18 W power, water level even with the level in test tube, centered in the bath. Check the sample every 15 min for 1 h. If big chunks persist, then monitor at 4, 8, 24 h, until these chunks disappear. Record this time and appearance of these samples, noting how they change. Take one of these samples immediately from previous step for UVVIS analysis. Using quartz cuvettes, record UVVIS spectra in the 3251400 nm range. Repeat after one hour, and calculate the dierence in the area under the curve from 700 to 1000 nm. This percentage dierence serves as a numerical measure of the suspension stability. Also, record the results of visual inspection of the suspension before and after the scans. The long-term stability is also monitored by visual inspection of this suspension over a period of one week or more. The spectral range of 7001000 nm was selected because it does not usually have strong features associated with particular types of nanotubes, therefore results are not dependent on the presence of these nanotube types in a particular sample.

Fig. 1. TGA mass loss and its derivative for three separate specimens of puried HiPco material (a) and corresponding raw nanotubes (b). Note the variability of data due to inhomogeneity of material.

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3. Results and discussion The results obtained when this protocol was applied to a puried and corresponding raw HiPco nanotube material are shown in Figs. 15. The TGA data in Fig. 1(a) indicates oxidation temperatures of 597, 599 and 609 C with residual masses being 0.8%, 0.6% and 0.4% respectively, resulting in To 602 6:5 C and Mr 0:59 0:18%. The sample exhibited only one exothermal event. The overall thermal stability is very good and residual mass is small. The excellent thermal stability indicates that the nanotubes are neither damaged nor derivatized by the purication process. Small standard deviations of the To and Mr are indicative of a good homogeneity of the sample. This can be compared to the Fig. 1(b). Raw HiPco material has oxidation temperatures of 404.5, 405.5 and 407.6 C with residual masses being 23.6%, 25.6% and 30.1% respectively, resulting in To 405:87 1:58 C and Mr 26:4 3:3%. Overall thermal stability is low and consistent with large amount of iron particles. Standard deviations of To and Mr are smaller than in puried specimen, indicative of better homogeneity. Upon closer examination of the TG traces, one can see that right after To they make an unexpected comeback, i.e. specimen temperature does not increase monotonically, but rather goes up and down. This eect is easier to see if TG traces are plotted vs. time [21]. At some point sudden drop in the specimen mass is accompanied by rapid increase in the sample

temperature by 20 C, followed by rapid decrease. This observation can be explained by spontaneous combustion of the nanotubes, i.e. when heat released in the exothermic reaction is enough to sustain rapid burning of the sample [27]. We frequently observe this behavior in unpuried uy SWCNT samples. The SEM data presented in Fig. 2(a) indicates rather uniform abundance of SWCNTs. The SEMEDS data (Fig. 2(c)) shows very little iron left. The presence of a strong chlorine signal is indicative of residual chlorine remaining in the sample after the HCl reux of the sample during purication. It is to be noted that the chlorine signal is mostly gone after repeated washings with water. The presence of a weak peak associated with silicon is attributable to the glassware. The origin of the weak copper peak is unknown. This is further conrmed in TEMEDS data shown in Fig. 3(c). The low magnication and high magnication TEM images (Fig. 3(a)) indicate very clean SWCNT surfaces devoid of amorphous coatings or surface irregularities that are some times seen after strong oxidation steps during purication procedures. This can be compared to the SEM and TEM images on Figs. 2(b) and 3(b). Raw HiPco material has uniform abundance of SWCNTs and large amount of iron clusters, which are also visible on EDS spectra (Fig. 2(d) and Fig. 3(d)). Raman data presented in Fig. 4 shows strong features in the radial breathing mode as well as tangential mode regions. The consistency of similar spectra from dierent

Fig. 2. SEM images of puried (a) and raw (b) HiPco material, and corresponding EDS spectra (c, d).

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Fig. 3. TEM images of puried (a) and raw (b) HiPco material, and corresponding EDS spectra (c, d). Cu peaks originate from the copper TEM grid.

16 14

25

Scattering intensity (arb. units)

12 10 8

Scattering intensity (arb. units)

20

15

200
6 4 2 0 1300

250

300

10

200

250
x10

300

0 1400 1500 1600 1300 1500 1600

(a)

Raman shift

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Raman shift (cm-1)

Fig. 4. Raman spectra of puried (a) and raw (b) HiPco material taken at three dierent locations. For comparison of both materials, the Raman spectra of puried HiPco (solid circles) are also included in (b). The 780 nm laser line was used for excitation. The radial breathing modes regions are given in the insets.

regions of the sample is indicative of good homogeneity of the sample. The D-band is at 1295 cm1 , only 30 cm1 broad (FWHM), giving convincing indication for SWCNT origin. The spectral region 13301500 cm1 is at and with almost baseline intensity, which supports the low amorphous carbon content. The Raman spectra

of puried HiPco and the corresponding raw material are compared in Fig. 4(b). It is clearly seen on the insets that purication preserves the variety of nanotube diameters observed in the as-grown sample. The abundance of the larger diameter nanotubes (lower frequency peaks), however, seems to increase. A slight upward

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0 hr 0.6 0.4 0.2 0.0 400 600 800

,nm

1 hr

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derivatization (via functional groups attached to SWCNTs) using such techniques as TGAIR and TGAMS. This JSC protocol standardizes the analytical procedures so that comparison of materials can be done with less ambiguity. This protocol is based on particular equipment used for characterization and may need to be modied when using other instruments. Future revisions will include additional techniques that can be used easily to establish the status of SWCNTs.

(a)
0.8

0 hr 0.6 0.4 0.2 0.0 400 600 1 hr

Acknowledgements Authors thank Carl Scott of NASA-JSC for discussion and critical review of the manuscript and Lou Hulse of G.B.Tech for SEM work. This work is supported by the State of Texas through TcSAM, NASA Cooperative Agreement NCC-1-02038 through TiiMS and NASA grant NAS9-19100.

(b)

800 ,nm

1000

1200

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Fig. 5. UVVIS spectra of puried (a) and raw (b) HiPco material suspended in DMF, taken immediately after sonication (0 h) and 1 h later.

References
[1] Dresselhaus MS, Dresselhaus G, Avouris P, editors. Carbon nanotubes: synthesis, structure, properties and applications. Topics in applied physics, vol. 80. Heidelberg: Springler-Verlag; 2000. [2] Yowell L, Files B, Scott C, Mayeaux B, Sullivan E, Arepalli S, et al. Nanotube composites and applications for human spaceight. AIAA IAC-02-IAA.12.1.01, 2002. [3] Yakobson BI, Smalley RE. Fullerene nanotubes: C1;000;000 and beyond. Amer Scientist 1997;85:32437. [4] Journet C, Maser WK, Bernier P, Loiseau A, de la Chapelle ML, Lefrant S, et al. Large-scale production of single-walled carbon nanotubes by the electric-arc technique. Nature 1998;388: 7568. [5] Guo T, Nikolaev P, Thess A, Colbert DT, Smalley RE. Catalytic growth of single-walled nanotubes by laser vaporization. Chem Phys Lett 1995;243:4954. [6] Nikolaev P, Bronikowski MJ, Bradley RK, Rohmund F, Colbert DT, Smith KA, et al. Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide. Chem Phys Lett 1999;313:917. [7] Cassell A, Franklin N, Chan E, Han J, Dai H. Directed growth of free-standing single-walled carbon nanotubes. J Am Chem Soc 1999;121:79756. [8] Itkis ME, Perea DE, Niyogi S, Rickard SM, Hamon MA, Hu H, et al. Purity evaluation of as-prepared single-walled carbon nanotube soot by use of solution-phase near-IR spectroscopy. Nano Lett 2003;3:30914. [9] Harutyunyan AR, Pradhan BK, Chang JP, Chen GG, Eklund PC. Purication of single-wall carbon nanotubes by selective microwave heating of catalyst particles. J Phys Chem B 2001;106:86715. [10] Chiang IW, Brinson BE, Smalley RE, Margrave JL, Hauge RH. Purication and characterization of single-wall carbon nanotubes. J Phys Chem B 2001;105:115761. [11] Moon J, An KH, Lee YH, Park YS, Bae DJ, Park GS. High-yield purication process of singlewalled carbon nanotubes. J Phys Chem B 2001;105:567781. [12] Gorelik O, Nikolaev P, Arepalli S. NASA contractor report, NASA/CR-208926, 2000.

shift of 12 cm1 of the G mode frequency of puried SWCNTs indicates weak protonation due to HCl reux. The overall spectral features of puried and as-grown SWCNTs are very similar, which further supports the conclusion that our purication route does not inict noticeable damage to nanotubes. The absorption spectra (Fig. 5(a)) of the puried material suspended in DMF was collected following the dispersability protocol mentioned in Section 2.5.5. The sample dispersed easily within a 15 min bath sonication and stayed well suspended after an hour (just 2.95% decrease in the area under the spectrum after 1 h). Raw material (Fig. 5(b)), on the other hand, took 30 min to disperse in DMF and did not form stable suspension (65.9% decrease in the area under the spectrum after 1 h). We have noticed that longer sonication, on the order of several hours, can improve the stability of the suspension. We can conclude that purication has greatly increased nanotubes ability to disperse and stay in DMF suspension.

4. Conclusions and future work A protocol for characterizing the carbon nanotube material is developed and is used for puried and raw HiPco material. Dierent analytical techniques are used successfully to determine the homogeneity, purity and thermal stability both qualitatively as well as quantitatively. It is possible that one can add additional procedures to monitor the state of oxidation, extent of

S. Arepalli et al. / Carbon 42 (2004) 17831791 [13] Rinzler AG, Liu J, Dai H, Nikolaev P, Human CB, RodriguezMarcias FG, et al. Large-scale purication of single-walled carbon nanotubes: process, product, and characterization. Appl Phys A 1998;67:2937. [14] Bandyopadhyaya R, Nativ-Roth R, Regev O, Yerushalmi-Rozen R. Stabilization of individual carbon nanotubes in aqueous solutions. Nano Lett 2002;1:258. [15] OConnell MJ, Bachilo SM, Human CB, Moore VC, Strano MS, Haroz EH, et al. Band gap uorescence from individual singlewalled carbon nanotubes. Science 2001;297:5936. [16] Henrard L, Popov VN, Rubio A. Inuence of packing on the vibrational properties of innite and nite bundles of carbon nanotubes. Phys Rev B 2001;64:20540313. [17] Jorio A, Souza-Filho AG, Dresselhaus G, Dresselhaus MS, Swan u MS, et al. G-band resonant Raman study of 62 isolated AK, Unl single-wall carbon nanotubes. Phys Rev B 2002;65:155412. [18] Hamon MA, Hui H, Bhowmik P, Itkis HME, Haddon RC. Esterfunctionalized soluble single-walled carbon nanotubes. Appl Phys A 2001;74:3338. [19] Park C, Ounaies Z, Watson KA, Crooks RE, Smith J, Lowther SE, et al. Dispersion of single wall carbon nanotubes by in situ polymerization under sonication. Chem Phys Lett 2002;364: 3038.

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[20] Rols S, Almairac R, Henrard L, Anglaret E, Sauvajol J-L. Diraction by nite-size crystalline bundles of single wall nanotubes. Euro Phys J B 1999;10:26370. [21] Nikolaev P, Gorelik O, Arepalli S. Carbon nanotubes characterization by TGA, in preparation. [22] Dresselhaus MS, Dresselhaus G, Eklund PC. Science of fullerenes and carbon nanotubes. New York: Academic Press; 1996. [23] Ferrari AC, Robertson J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 2000;61:14095 107. [24] Jorio A, Fantini C, Dantas MSS, Pimenta MA, Souza-Filho AG, Samsonidze GG, et al. Linewidth of the Raman features of individual single-wall carbon nanotubes. Phys Rev B 2002;66: 1154119. [25] Brown SDM, Jorio A, Dresselhaus MS, Dresselhaus G. Observations of the D-band feature in the Raman spectra of carbon nanotubes. Phys Rev B 2001;64:0734037. [26] Wang Y, Alsmeyer DC, McCreery RL. Raman spectroscopy of carbon materials: structural basis of observed spectra. Chem Mater 1990;2:55763. [27] Ajayan PM, Terrones M, de la Guardia A, Huc V, Grobert N, Wei BQ, et al. Nanotubes in a ash-ignition and reconstruction. Science 2001;296:705.