Winey, Karen I
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PublicationAn infiltration method for preparing single-wall nanotube/epoxy composites with improved thermal conductivity(2006-04-13) Du, Fangming; Guthy, Csaba; Fischer, John E; Kashiwagi, Takashi; Winey, Karen IRecent studies of SWNT/polymer nanocomposites identify the large interfacial thermal resistance at nanotube/nanotube junctions as a primary cause for the only modest increases in thermal conductivity relative to the polymer matrix. To reduce this interfacial thermal resistance, we prepared a freestanding nanotube framework by removing the polymer matrix from a 1 wt % SWNT/PMMA composite by nitrogen gasification and then infiltrated it with epoxy resin and cured. The SWNT/epoxy composite made by this infiltration method has a micron-scale, bicontinuous morphology and much improved thermal conductivity (220% relative to epoxy) due to the more effective heat transfer within the nanotube-rich phase. By applying a linear mixing rule to the bicontinuous composite, we conclude that even at high loadings the nanotube framework more effectively transports phonons than well-dispersed SWNT bundles. Contrary to the widely accepted approaches, these findings suggest that better thermal and electrical conductivities can be accomplished via heterogeneous distributions of SWNT in polymer matrices. PublicationPolarized spectroscopy of aligned single-wall carbon nanotubes(2000-11-15) Hwang, J.; Gommans, H. H.; Ugawa, A.; Tashiro, H.; Winey, Karen I; Haggenmueller, Reto; Fischer, John E; Tanner, D. B.; Rinzler, A. G.Polarized resonant Raman and optical spectroscopy of aligned single-wall carbon nanotubes show that the optical transitions are strongly polarized along the nanotubes axis. This behavior is consistent with recent electronic structure calculations. PublicationInterfacial in situ polymerization of single wall carbon nanotube/nylon 6,6 nanocomposites(2006-03-22) Haggenmueller, Reto; Du, Fangming; Fischer, John E.; Winey, Karen IAn interfacial polymerization method for nylon 6,6 was adapted to produce nanocomposites with single wall carbon nanotubes (SWNT) via in situ polymerization. SWNT were incorporated in purified, functionalized or surfactant stabilized forms. The functionalization of SWNT was characterized by FTIR, Raman spectroscopy and TGA and the SWNT dispersion was characterized by optical microscopy before and after the in situ polymerization. SWNT functionalization and surfactant stabilization improved the nanotube dispersion in solvents but only functionalized SWNT showed a good dispersion in composites, whereas purified and surfactant stabilized SWNT resulted in poor dispersion and nanotube agglomeration. Weak shear flow induced SWNT flocculation in these nanocomposites. The electrical and mechanical properties of the SWNT/nylon nanocomposites are briefly discussed in terms of SWNT loading, dispersion, length and type of functionalization. PublicationPharmacokinetic and behavioral characterization of a longterm antipsychotic delivery system in rodents and rabbits(2007-02-01) Metzger, Kayla L; Shoemaker, Jody M; Kahn, Jonathan B; Maxwell, Christina R; Liang, Yuling; Tokarczyk, Jan; Kanes, Stephen J; Hans, Meredith; Lowman, Anthony M; Winey, Karen I; Dan, Nily; Siegel, Steven J; Swerdlow, Neal RRationale: Non-adherence with medication remains the major correctable cause of poor outcome in schizophrenia. However, few treatments have addressed this major determinant of outcome with novel long-term delivery systems. Objectives: The aim of this study was to provide biological proof of concept for a long-term implantable antipsychotic delivery system in rodents and rabbits. Materials and methods: Implantable formulations of haloperidol were created using biodegradable polymers. Implants were characterized for in vitro release and in vivo behavior using prepulse inhibition of startle in rats and mice, as well as pharmacokinetics in rabbits. Results: Behavioral measures demonstrate the effectiveness of haloperidol implants delivering 1 mg/kg in mice and 0.6 mg/kg in rats to block amphetamine (10 mg/kg) in mice or apomorphine (0.5 mg/kg) in rats. Additionally, we demonstrate the pattern of release from single polymer implants for 1 year in rabbits. Conclusions: The current study suggests that implantable formulations are a viable approach to providing long-term delivery of antipsychotic medications in vivo using animal models of behavior and pharmacokinetics. In contrast to depot formulations, implantable formulations could last 6 months or longer. Additionally, implants can be removed throughout the delivery interval, offering a degree of reversibility not available with depot formulations. PublicationControlling the In Vitro Release Profiles for a System of Haloperidol-Loaded PLGA(2007-06-11) Siegel, Steven J; Budhian, Avinash; Winey, Karen IWe have used a systematic methodology to tailor the in vitro drug release profiles for a system of PLGA/PLA nanoparticles encapsulating a hydrophobic drug, haloperidol. We applied our previously developed sonication and homogenization methods to produce haloperidol-loaded PLGA/PLA nanoparticles with 200–1000 nm diameters and 0.2–2.5% drug content. The three important properties affecting release behavior were identified as: polymer hydrophobicity, particle size and particle coating. Increasing the polymer hydrophobicity reduces the initial burst and extends the period of release. Increasing the particle size reduces the initial burst and increases the rate of release. It was also shown that coating the particles with chitosan significantly reduces the initial burst without affecting other parts of the release profile. Various combinations of the above three properties were used to achieve in vitro release of drug over a period of 8, 25 and >40 days, with initial burst <25% and a steady release rate over the entire period of release. Polymer molecular weight and particle drug content were inconsequential for drug release in this system. Experimental in vitro drug release data were fitted with available mathematical models in literature to establish that the mechanism of drug release is predominantly diffusion controlled. The average value of drug diffusivities for PLGA and PLA nanoparticles was calculated and its variation with particle size was established. PublicationSmall angle neutron scattering from single-wall carbon nanotube suspensions: evidence for isolated rigid rods and rod networks(2004-01-19) Zhou, Wei; Islam, M. F; Wang, H.; Ho, D. L; Winey, Karen I; Yodh, A. G; Fischer, John EWe report small angle neutron scattering (SANS) from dilute suspensions of purified individual single wall carbon nanotubes (SWNTs) in D2O with added sodium dodecylbenzene sulfonate (NaDDBS) ionic surfactant. The scattered intensity scales as Q-1 for scattered wave vector, Q, in the range 0.005 < Q < 0.02 Å-1. The Q-1 behavior is characteristic of isolated rigid rods. A crossover of the scattered intensity power law dependence from Q-1 to Q-2 is observed at ~0.004 Å-1, suggesting the SWNTs form a loose network at 0.1 wt% with a mesh size of ~160 nm. SANS profiles from several other dispersions of SWNTs do not exhibit isolated rigid rod behavior; evidently the SWNTs in these systems are not isolated and form aggregates. PublicationCellular Structures of Carbon Nanotubes in a Polymer Matrix Improve Properties Relative to Composites with Dispersed Nanotubes(2008-03-03) Mu, Minfang; Walker, Amanda M; Torkelson, John M; Winey, Karen IA new processing method has been developed to combine a polymer and single wall carbon nanotubes (SWCNTs) to form electrically conductive composites with desirable rheological and mechanical properties. The process involves coating polystyrene (PS) pellets with SWCNTs and then hot pressing to make a contiguous, cellular SWCNT structure. By this method, the electrical percolation threshold decreases and the electrical conductivity increases significantly as compared to composites with a well-dispersed SWCNTs. For example, a SWCNT / PS composite with 0.5 wt% nanotubes and made by this coated particle process (CPP) has an electrical conductivity of ~ 3 x 10-4 S/cm, while a well-dispersed composite made by a coagulation method with the same SWCNT amount has an electrical conductivity of only ~ 10-8 S/cm. The rheological properties of the composite with a macroscopic cellular SWCNT structure are comparable to PS, while the well-dispersed composite exhibits a solid-like behavior, indicating that composites made by this new CPP method are more processable. In addition, the mechanical properties of the CPP-made composite decrease only slightly, as compared with PS. Relative to the common appoach of seeking better dispersion, this new fabrication method provides an important alternative means to higher electrical conductivity in SWCNT / polymer composites. Our straightforward particle coating and pressing method avoids organic solvents and is suitable for large-scale, inexpensive processing using a wide variety of polymer and nanoparticles. PublicationSingle Wall Carbon Nanotube Fibers Extruded from Super-Acid Suspensions: Preferred Orientation, Electrical and Thermal Transport(2004-01-15) Zhou, Wei; Vavro, Juraj; Winey, Karen I; Guthy, K.; Fischer, John E; Ericson, Lars M; Ramesh, Sivarajan; Saini, Rajesh K; Davis, Virginia A; Kittrell, Carter; Pasquali, M.; Hauge, Robert H; Smalley, Richard EFibers of single wall carbon nanotubes extruded from super-acid suspensions exhibit preferred orientation along their axes. We characterize the alignment by x-ray fiber diagrams and polarized Raman scattering, using a model which allows for a completely unaligned fraction. This fraction ranges from 0.17 to 0.05±0.02 for three fibers extruded under different conditions, with corresponding Gaussian full widths at half-maximum (FWHM) from 64o to 44o±2o. FWHM, aligned fraction, electrical and thermal transport all improve with decreasing extrusion orifice diameter. Resistivity, thermoelectric power and resonant-enhanced Raman scattering indicate that the neat fibers are strongly p-doped; the lowest observed ρ is 0.25mΩcm at 300 K. High temperature annealing increases ρ by more than 1 order of magnitude and restores the Raman resonance associated with low-energy van Hove transitions, without affecting the nanotube alignment. PublicationTemperature Dependence of Thermal Conductivity Enhancement in Single-walled Carbon Nanotube/polystyrene Composites(2010-02-23) Jakubinek, Michael B; White, Mary Anne; Mu, Minfang; Winey, Karen IThe thermal conductivity of single-walled carbon nanotube (SWCNT)/polystyrene composites, prepared by a method known to produce a uniform distribution of SWCNT bundles on the micrometer length scale, was measured in the temperature range from approximately 140 to 360 K. The thermal conductivity enhancement (50% for 1 mass % at 300 K) is reasonably constant above room temperature but is reduced at the lower temperatures. This result is consistent with the expected, large contribution of interfacial thermal resistance in SWCNT/polymer composites. Enhancements in electrical conductivity show that 1 mass % loading is in the region of the electrical percolation threshold. PublicationA Coagulation Method to Prepare Single-Walled Carbon Nanotube/PMMA Composites and Their Modulus, Electrical Conductivity, and Thermal Stability(2003-12-15) Fischer, John E; Du, Fangming; Winey, Karen IA coagulation method that provides better dispersion of SWNT in the polymer matrix has been used to produce single-walled carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) composites. Optical microscopy and SEM show improved dispersion of SWNT in the PMMA matrix, which is a key factor in composite performance. Aligned and unaligned composites were made with purified SWNT with different SWNT loadings, from 0.1 to 7 wt%. Comprehensive testing shows improved elastic modulus, electrical conductivity, and thermal stability with addition of SWNT. The electrical conductivity of a 2 wt% SWNT composite decreases significantly (>105), when the SWNT is aligned and this result is discussed in terms of percolation.