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  1. Abstract

    Determining the relative energies of transport states in organic semiconductors is critical to understanding the properties of electronic devices and in designing device stacks. Futhermore, defect states are also highly important and can greatly impact material properties and device performance. Recently, energy‐resolved electrochemical impedance spectroscopy (ER‐EIS) is developed to probe both the ionization energy (IE) and electron affinity (EA) as well as sub‐bandgap defect states in organic semiconductors. Herein, ER‐EIS is compared to cyclic voltammetry (CV) and photoemission spectroscopies for extracting IE and EA values, and to photothermal deflection spectroscopy (PDS) for probing defect states in both polymer and molecular organic semiconductors. The results show that ER‐EIS determined IE and EA are in better agreement with photoemission spectroscopy measurements as compared to CV for both polymer and molecular materials. Furthermore, the defect states detected by ER‐EIS agree with sub‐bandgap features detected by PDS. Surprisingly, ER‐EIS measurements of regiorandom and regioregular poly(3‐hexylthiophene) (P3HT) show clear defect bands that occur at significantly different energies. In regioregular P3HT the defect band is near the edge of the occupied states while it is near the edge of the unoccupied states in regiorandom P3HT.

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  2. Abstract

    Hydraulic fracturing of oil and gas wells is a water intensive process. Limited availability, cost and increasing government regulations restraining the use and disposal of fresh water have led to the need for alternative fracturing fluids. Using CO2 foam as a fracturing fluid can drastically reduce the need for water in hydraulic fracturing. We address the addition of polyelectrolyte complex nanoparticles (PECNP) to surfactant solutions to improve foam stability, durability and rheological properties at high foam qualities. Polyelectrolyte pH and polyanion/polycation ratios were varied to minimize particle size and maximize absolute zeta potential of the resulting nanoparticles. Rheological tests were conducted on foam systems of varying surfactant/PECNP ratios and different foam quality to understand the effect of shear on viscosity under simulated reservoir conditions of 40°C and 1300 psi. The same foam systems were tested for stability and durability in a view cell at reservoir conditions. Supercritical CO2 foam generated by surfactant alone resulted in short lived, low viscosity foam because of surfactant drainage from foam lamellae. However, addition of PECNP strengthens the foam film by swelling the film due to increased osmotic pressure and electrostatic forces. Electrostatic interactions reduce dynamic movement of surfactant micelles, thereby stabilizing the foam lamellae, which imparts high durability and viscosity to supercritical CO2 foams. From the rheology test results, it was concluded that increasing foam quality and the presence of PECNP resulted in improved viscosity. Also, foam systems with PECNP showed promising results compared with foam generated using surfactant alone in the view cell durability test. The addition of optimized polyelectrolyte nanoparticles to the surfactant can improve viscosity and durability of supercritical CO2 foam during hydraulic fracturing, which can lead to large reductions in water requirements.

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    Precipitate scale formation is a major issue for the oil industry, plugging equipment, and reservoirs and resulting in increased operational costs. Poly(vinyl sulfonate) (PVS) is often used as a scale inhibitor to prevent the formation of barium sulfate scale. However, PVS effectiveness is limited by its short lifetime in reservoir. In this article, PVS has been entrapped in polyelectrolyte complex nanoparticles (PECNPs), altering its charge and thus enabling improved adsorption on the rock surface. As the ionic strength of the surrounding brine increases, the PVS is then released from the PECNPs, making it available to inhibit scale formation gradually. Positively charged PECNPs were made using a combination of poly(ethyleneimine) (PEI) and PVS. After NPs optimization, static adsorption tests were performed, which confirm the nanoparticles' rapid and strong adsorption. An increase in the ionic strength of the displacing fluid was used to decompose the PECNPs structure and release the PVS into solution. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2019,136, 47225.

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