Carbon nanotubes: measuring dispersion and length.

Advanced technological uses of single-walled carbon nanotubes (SWCNTs) rely on the production of single length and chirality populations that are currently only available through liquid-phase post processing. The foundation of all of these processing steps is the attainment of individualized nanotube dispersions in solution. An understanding of the colloidal properties of the dispersed SWCNTs can then be used to design appropriate conditions for separations. In many instances nanotube size, particularly length, is especially active in determining the properties achievable in a given population, and, thus, there is a critical need for measurement technologies for both length distribution and effective separation techniques. In this Progress Report, the current state of the art for measuring dispersion and length populations, including separations, is documented, and examples are used to demonstrate the desirability of addressing these parameters.

Length distribution of single-walled carbon nanotubes in aqueous suspension measured by electrospray differential mobility analysis.

The first characterization of the length distribution of single-walled carbon nanotubes (SWCNT) dispersed in a liquid by electrospray differential mobility analysis (ES-DMA) is presented. Although an understanding of geometric properties of SWCNTs, including length, diameter, aspect ratio, and chirality, is essential for commercial applications, rapid characterization of nanotube length distributions remains challenging. Here the use of ES-DMA to obtain length distributions of DNA-wrapped SWCNTs dispersed in aqueous solutions is demonstrated. Lengths measured by ES-DMA compare favorably with those obtained from multiangle light scattering, dynamic light scattering, field flow fractionation with UV/vis detection, and atomic force microscopy, validating ES-DMA as a technique to measure SWCNTs of <250 nm in length. The nanotubes are previously purified and dispersed by wrapping with oligomeric DNA in aqueous solution and centrifuging to remove bundles and amorphous carbon. These dispersions are particularly attractive due to their amenability to bulk processing, ease of storage, high concentration, compatibility with biological and high-throughput manufacturing environments, and for their potential applications ranging from electronics and hydrogen-storage vessels to anticancer agents.

Centrifugal length separation of carbon nanotubes.

Separation of single-wall carbon nanotubes (SWCNTs) by length via centrifugation in a high density medium, and the characterization of both the separated fractions and the centrifugation process are presented. Significant quantities of the separated SWCNTs ranging in average length from <50 nm to approximately 2 microm were produced, with the distribution width being coupled to the rate of the separation. Less rapid separation is shown to produce narrower distributions; these length fractions, produced using sodium deoxycholate dispersed SWCNTs, were characterized by UV-visible-near-infrared absorption and fluorescence spectroscopy, dynamic light scattering, Raman scattering, and atomic force microscopy. Several parameters of the separation were additionally explored: SWCNT concentration, added salt concentration, liquid density, rotor speed, surfactant concentration, and the processing temperature. The centrifugation technique is shown to support 10 mg per day scale processing and is applicable to all of the major SWCNT production methods. The cost per unit of the centrifugation-based separation is also demonstrated to be significantly less than size exclusion chromatography-based separations.

Size separation of single-wall carbon nanotubes by flow-field flow fractionation.

Flow-field flow fractionation (flow-FFF) is used to separate single wall carbon nanotubes (SWNTs) dispersed in aqueous medium by the use of DNA. Online measurements are made of SWNT concentration, molar mass, and size by using UV-vis absorption and multiangle light scattering (MALS). Separations are made of both unfractionated SWNTs and SWNT fractions made by use of size exclusion chromatography (SEC). The SEC fractions are well resolved by flow-FFF. SWNT hydrodynamic volume from calibrations with polymer latex particles in flow-FFF are compared to calibrations of hydrodynamic volume from the SEC fractions derived from dissolved polymers. Rod lengths of the SWNTs are calculated from online measurements of MALS and those are compared to rod lengths from hydrodynamic models based on latex sphere calibrations. Samples with varied sizes were prepared by fracturing SWNTs through extended sonication. Flow-FFF of these fractured samples shows very broad size distributions compared to the original SEC and flow-FFF fractions.

Length-dependent optical effects in single-wall carbon nanotubes.

Among the novel chemical and physical attributes of single-wall carbon nanotubes (SWCNTs), the optical properties are perhaps the most compelling. Although much is known about how such characteristics depend on nanotube chirality and diameter, relatively little is known about how the optical response depends on length, the next most obvious and fundamental nanotube trait. We show here that the intrinsic optical response of single-wall carbon nanotubes exhibits a strong dependence on nanotube length, and we offer a simple explanation that relates this behavior to the localization of a bound exciton along the length of a nanotube. The results presented here suggest that, for a given volume fraction, the longest nanotubes display significantly enhanced absorption, near-infrared fluorescence, and Raman scattering, which has important practical implications for potential applications that seek to exploit the unique optical characteristics of SWCNTs.

Characterization of pore structure in a nanoporous low-dielectric-constant thin film by neutron porosimetry and X-ray porosimetry.

A small-angle neutron scattering (SANS) porosimetry technique is presented for characterization of pore structure in nanoporous thin films. The technique is applied to characterize a spin-on organosilicate low dielectric constant (low-k) material with a random pore structure. Porosimetry experiments are conducted using a "contrast match" solvent (a mixture of toluene-d8 and toluene-h8) having the same neutron scattering length density as that of the nanoporous film matrix. The film is exposed to contrast match toluene vapor in a carrier gas (air), and pores fill with liquid by capillary condensation. The partial pressure of the solvent vapor is increased stepwise from 0 (pure air) to P0 (saturated solvent vapor) and then decreased stepwise to 0 (pure air). As the solvent partial pressure increases, pores fill with liquid solvent progressively from smallest to largest. SANS measurements quantify the average size of the empty pores (those not filled with contrast match solvent). Analogous porosimetry experiments using specular X-ray reflectivity (SXR) quantify the volume fraction of solvent adsorbed at each step. Combining SXR and SANS data yields information about the pore size distribution and illustrates the size dependence of the filling process. For comparison, the pore size distribution is also calculated by application of the classical Kelvin equation to the SXR data.

Characterization of nanoporous low-k thin films by small-angle neutron scattering contrast variation.

Small-angle neutron scattering contrast variation is applied to characterization of nanoporous low-dielectric constant (low-k) thin films. Films are exposed to saturated solvent vapor in air, whereby the pores fill with liquid by capillary condensation. The pores are filled with mixtures of hydrogen- and deuterium-containing solvents to vary the neutron contrast with the matrix (wall). The composition of the solvent mixture is systematically varied to identify a composition that minimizes the scattered intensity (contrast match point). From the contrast match point composition, film characteristics including matrix density and homogeneity are assessed. Four spin-on low-k materials including a methylsilsesquioxane, an organic polymer, a xerogel, and a hydrogensilsesquioxane are characterized by the new technique. Calculated matrix mass densities are compared to independent density measurements obtained by an established specular X-ray reflectivity technique. We find no evidence of "closed pores", defined here as pores inaccessible to the probe solvent, in any of the materials studied.

Tri-alpha-naphthylbenzene as a crystalline or glassy matrix for matrix-assisted laser desorption/ionization: a model system for the study of effects of dispersion of polymer samples at a molecular level.

Tri-alpha-naphthylbenzene (TalphaNB) can exist as either a crystalline or glassy solid at ambient temperatures, making it a unique matrix in matrix-assisted laser desorption/ionization (MALDI) spectroscopy. Electrosprayed TalphaNB is crystalline and has a melting point of 180 +/- 2 degrees C, as measured by differential scanning calorimetry (DSC). A glass of TalphaNB is obtained upon heating above the crystalline melting point with a glass transition temperature of 68 +/- 2 degrees C having no remaining crystallinity. MALDI samples containing mass fraction 1% polystyrene (PS) are run in both the crystalline and amorphous states. In the crystalline state, there is a strong spectrum typical of PS, but upon melting and quenching to the glassy state, the MALDI signal disappears. If the transparent, amorphous sample is treated with 1-butanol, it becomes white, and the MALDI signal returns. DSC shows that the 1-butanol treatment leads to the return of some of the crystallinity. Small angle neutron scattering (SANS) shows that the crystalline state has large aggregations of PS while the amorphous state has molecularly dispersed PS molecules. MALDI gives strong signals only when there are large aggregations of polymer molecules, with individually dispersed molecules producing no signal.

Small angle neutron scattering measurements of synthetic polymer dispersions in matrix-assisted laser desorption/ionization matrixes.

Small angle neutron scattering (SANS) is used to measure the size and the dispersion of synthetic polymers in matrix-assisted laser desorption/ionization (MALDI) matrixes. Deuterated polystyrene (DPS) and dithranol in tetrahydrofuran were deposited by electrospray onto a substrate for small angle neutron scattering (SANS) measurements. DPS with 6050 and 27,000 g mol(-1) molecular masses were prepared at mass fractions between 0.2 and 6%. All samples contained large aggregates of DPS with characteristic sizes >200 A that represent hundreds of aggregated chains. Samples of mass fraction 1% DPS (6050 g mol(-1)) in 2,5-dihydroxybenzoic acid, all-trans-retinoic acid, and sinapinic acid also have large zero angle scattering characteristic of large aggregates. The morphological trend obtained from the SANS measurements of the DPS aggregate size in the four matrixes is dithranol > 2,5-dihydroxybenzoic acid > all-trans-retinoic acid > sinapinic acid. These measurements indicate that DPS in dithranol exhibits the most strong phase separation, while DPS in sinapinic acid shows considerable domain mixing. All of these matrixes produce MALDI signal strength under appropriate conditions, suggesting that strong phase separation does not diminish the signal-to-noise ratio. DPS (188,000 g mol(-1)) in biphenyl was used as a model system of a matrix that can be either crystalline or amorphous. SANS data shows that above the biphenyl melting point, a conventional solution is formed that has molecularly dispersed polymers. Upon crystallization, there is strong aggregation of the DPS into large domains. Therefore, the crystalline matrixes commonly used in MALDI measurements probably cause large aggregations of polymers to be present during the MALDI process.