Barry J. Bauer

A SAXS study of the internal structure of dendritic polymer systems

Small-angle x-ray scattering was used to characterize the single-particle scattering factors produced by poly(amidoamine) dendrimers, poly(propleneimine) dendrimers, and polyol hyperbranched polymers in dilute solutions with methanol as solvent. Fits from electron density modeling reveal similar overall densities of the dendrimers as a function of dendrimer generation. The seventh through tenth generation poly(amidoamine) dendrimers exhibit higher order scattering features that require nearly monodisperse, spherical particles with essentially uniform internal segment densities. Dilute hyperbranched polymer solutions exhibit scattering more indicative of the inherent irregularity of internal segment densities and overall sizes to be expected within these systems. Radii of gyration estimated from electron density modeling agree reasonably well with those estimated by standard Guinier methods used in previous studies.

Temperature, composition and molecular-weight dependence of the binary interaction parameter of polystyrene/poly(vinyl methyl ether) blends

Abstract The binary interaction parameter χ eff has been obtained for deuterated polystyrene/poly(vinyl methyl ether) blends as a function of temperature, composition and molecular weight from small-angle neutron scattering experiments. The consistency of the correlation length ξ, the zero-wavenumber scattering intensity S (0) and the χ eff parameter with the mean-field prediction has been demonstrated by the q dependence of the static structure factor S ( q ) and the 1/T dependence of ξ −2 , S (0) −1 and χ eff . The effective interaction parameter χ eff can be related to the Flory-Huggins interaction parameter χ eff can be related to the Flory-Huggins interaction parameter χ F . The free-energy function as well as the spinodal curve and cloud-point curve have been constructed.

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.

Structural characterization of porous low-k thin films prepared by different techniques using x-ray porosimetry

Three different types of porous low-k dielectric films, with similar dielectric constants, are characterized using x-ray porosimetry (XRP). XRP is used to extract critical structural information, such as the average density, wall density, porosity, and pore size distribution. The materials include a plasma-enhanced-chemical-vapor-deposited carbon-doped oxide film composed of Si, C, O, and H (SiCOH) and two spin cast silsesquioxane type films—methylsilsesquioxane with a polymeric porogen (porous MSQ) and hydrogensilsesquioxane with a high boiling point solvent (porous HSQ). The porous SiCOH film displays the smallest pore sizes, while porous HSQ film has both the highest density wall material and porosity. The porous MSQ film exhibits a broad range of pores with the largest average pore size. We demonstrate that the average pore size obtained by the well-established method of neutron scattering and x-ray reflectivity is in good agreement with the XRP results.

Shear stabilization of critical fluctuations in bulk polymer blends studied by small angle neutron scattering

The small angle neutron scattering (SANS) technique has been used to study the concentration fluctuations of binary polymer mixtures under shear. Two different polymer systems, deuterated polystyrene/poly(vinylmethylether) and deuterated polystyrene/polybutadiene, have been studied as a function of temperature and shear rate. Due to the small wavelength of the incident neutron radiation compared with light, the shear dependence of concentration fluctuations in the one‐phase region and in the strong shear limit has been obtained from the q dependence of the scattering structure factor for the first time. From a detailed analysis of the scattering structure factor S(q) a crossover value of the wave number qs has been obtained as a function of temperature and shear rate. This crossover wave number represents the inverse of the lowest fluctuation mode which is not affected by shear. The temperature, viscosity, and shear rate dependence of this experimentally determined qs agree well with a simple rotatory dif...

Rheo-optical studies of carbon nanotube suspensions.

We use a polarization-modulation technique to investigate the optical anisotropy of multi- and single-wall carbon nanotubes suspended in a variety of solvents under simple shear flow. Measurements of birefringence and dichroism are performed as a function of shear rate, tube concentration, and solvent viscosity. At fixed volume fraction, the anisotropy increases with increasing shear stress due to enhanced flow alignment. At fixed shear stress, the anisotropy increases with volume fraction due to rotational excluded-volume interactions. By considering the rotational diffusivity as a function of nanotube length, diameter, concentration, and solvent viscosity, we demonstrate a leading-order scaling relation for the optical anisotropy in terms of rotary Peclet number Pe. At low Pe, our results are in qualitative agreement with the theoretical predictions of Doi and Edwards. At high Pe, our data suggest that the degree of nanotube alignment scales as Pe16.

Epoxy/SiO2 interpenetrating polymer networks

We demonstrate a potentially useful method of generating an SiO2 morphology, in situ, with interpenetrating polymer networks (IPN) chemistry. Organic/inorganic IPNs were synthesized with an organic phase made of epoxy resin and an SiO2 phase made by sol—gel chemistry. The two types of polymerization used were sequential and simultaneous with SiO2 content ranging from 0.02 to 0.43 g SiO2/g total weight. The resultant morphologies were examined by small angle X-ray scattering and transmission electron microscopy. The sequential IPNs were strongly phase separated into a finely divided SiO2 phase of ∼10 nm size scale. The simultaneous IPNs were weakly phase separated with considerable mixing in the phases. Thermal studies showed increased thermal stability for the IPNs, compared with unfilled epoxies or physically mixed silica filled epoxies.

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.

Network structure of epoxies — a neutron scattering study: 2

Abstract Neutron scattering measurements were performed on epoxies to elucidate the molecular network structure of these commonly used thermosets. A partially deuterated diglycidyl ether of bisphenol A (DGEBA) was cured with di- and triamines based on poly(propylene oxide) chains. Pronounced neutron scattering peaks were observed on all three epoxies studied, while X-ray scattering yielded scattering typical of most amorphous materials. The neutron scattering results can be explained successfully using equations that have been derived using a result from a random phase approximation based on an ideal network. Neutron measurements were also conducted on epoxies that had been swollen in acetone. The swollen sample results, along with those from the bulk specimens, provide a unique approach to the network homogeneity problem in epoxies.