From Silver Nanoparticles to Thin Films: Evolution of Microstructure and Electrical Conduction

Silver nanoparticles embedded in a dielectric matrix are investigated for their potential as broadband-absorbing optical sensor materials. This contribution focuses on the electrical properties of silver nanoparticles at various morphological stages. The electrical current through thin films, consisting of silver nanoparticles, was characterized as a function of film thickness. Three distinct conductivity zones were observed. Two relatively flat zones ("dielectric" for very thin films and "metallic" for films thicker than 300 - 400 {\AA}) are separated by a sharp transition zone where percolation dominates. The dielectric zone is characterized by isolated particle islands with the electrical conduction dominated by a thermally activated tunneling process. The transition zone is dominated by interconnected silver nanoclusters - a small increase of the film thickness results in a large increase of the electrical conductivity. The metallic conductivity zone dominates for thicknesses above 300 - 400 {\AA}

Infrared and photoelectron spectroscopy study of vapor phase deposited poly (3-hexylthiophene)

Poly (3-hexylthiophene) (P3HT) was thermally evaporated and deposited in vacuum. Infrared spectroscopy was used to confirm that the thin films were indeed P3HT, and showed that in-situ thermal evaporation provides a viable route for contaminant-free surface/interface analysis of P3HT in an ultrahigh vacuum (UHV) environment. Ultraviolet photoelectron spectroscopy (UPS) as well as X-ray photoelectron spectroscopy (XPS) experiments were carried out to examine the frontier orbitals and core energy levels of P3HT thin films vapor deposited in UHV on clean polycrystalline silver (Ag) surfaces. UPS spectra enable the determination of the vacuum shift at the polymer/metal interface, the valence band maximum (VBM), and the energy of the \Pi-band of the overlayer film. The P3HT vacuum level decreased in contrast to that of the underlying Ag as the film thickness increased. XPS and UPS data confirmed the chemical integrity (stoichiometry) of the polymer at high coverage, as well as the shift of the C 1s and S 2p binding energy peaks and the secondary-electron edge with increasing film thickness, indicating that band bending is present at the P3HT/Ag interface and that the measured onset of the valence band is about 0.8 +- 0.05 eV relative to the Fermi level

Identification of Minor Dye Components of Fibers via Integrating-Cavity-Enhanced Raman Spectroscopy

The goal of this project was to evaluate integrating-cavity-enhanced Raman spectroscopy (ICERS) for its potential to significantly enhance the signal strength while simultaneously removing the fluorescence, thus enhancing the signal-to-noise ratio (S/N), allowing for the identification of minor dye components on fibers

From silver nanoparticles to thin films: Evolution of microstructure and electrical conduction on glass substrates

Silver nanoparticles embedded in a dielectric matrix are investigated for their potential as broadband-absorbing optical sensor materials. This contribution focuses on the electrical properties of silver nanoparticles on glass substrates at various morphological stages. The electrical current through thin films, consisting of silver nanoparticles, was characterized as a function of film thickness. Three distinct conductivity zones were observed. Two relatively flat zones ("dielectric" for very thin films and "metallic" for films thicker than 300-400 angstrom) are separated by a sharp transition zone where percolation dominates. The dielectric zone is characterized by isolated particle islands with the electrical conduction dominated by a thermally activated tunneling process. The transition zone is dominated by interconnected silver nanoclusters-a small increase of the film thickness results in a large increase of the electrical conductivity. The metallic conductivity zone dominates for thicknesses above 300-400 angstrom. (C) 2008 Elsevier Ltd. All rights reserved

Electrical conductivity of thin-film composites containing silver nanoparticles embedded in a dielectric fluoropolymer matrix

Thin-film nanocomposites, consisting of silver nanoparticles embedded in a dielectric fluoropolymer matrix (poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene]), were synthesized using vapor-phase co-deposition. The electrical conductivity of these composites was measured in-situ as a function of film thickness at various metal concentrations. At low metal concentrations ( 90%), fragmented fractal nanoclusters were able to further interconnect to achieve the percolation process and eventually evolve into a metallic continuum with dielectric polymer inclusions. (c) 2008 Elsevier B.V. All rights reserved

Initial mechanisms for the dissociation of carbon from electronically-excited nitrotoluene molecules

We calculated the photoinduced decomposition of various nitrotoluene molecules, resulting in the formation of atomic carbon, at the B3LYP/6-311++G(d,p) level of theory using Gaussian 09. In addition, we used TD-DFT (B3LYP/6-311++G(d,p)) to calculate the excitation energies. The results confirm our previously reported experimental results. Specifically, we show that the absorption of 226 nm (5.49 eV) light can lead to the decomposition of nitrotoluene molecules and the formation of atomic carbon. One 226 nm photon is sufficient for the dissociation of carbon from 2-NT and 4-NT molecules. During the dissociation process, the CH3 group provides the dissociated carbon atom and the NO2 group accepts the H atoms from either the CH3 group or the benzene ring before carbon exits the molecular system. For the second and third carbon dissociation of 2-NT, the energy barriers are 6.70 eV and 7.43 eV, respectively, and two 226 nm photons would need to be absorbed by the molecule. If extra NO is present during the first carbon dissociation of 2-NT, it gets involved in the last two decomposition steps and forms a C=NH-N=O structure which stabilizes the decomposition products and lowers the energy barrier from 5.22 eV to 4.70 eV. However, for the second and third carbon dissociation of 2-NT, the NO molecules have no apparent effect. For nitrotoluene molecules with two or three NO2 groups (i.e., 2,4-DNT, 2,6-DNT, 3,4-DNT, and 2,4,6-TNT), the first carbon dissociation energies are between 5.26 eV and 5.57 eV. The carbon dissociation pathways for these molecules are similar to those of 2-NT. In 2,4-DNT, the lowest energy barriers for the second and third carbon dissociation are 6.54 eV and 6.60 eV, respectively, which are about 1 eV higher than the energy barrier for the first carbon dissociation. In case of 2,4-DNT/NO and 2,4,6-TNT/NO, NO acts as a catalyst in the first carbon dissociation processes and forms a C=NH-N=O structure which lowers the energy barriers by 0.48 eV and 0.89 eV, respectively

Development of an Environmentally Acceptable Hydraulic Fluid

Hydroelectric plants operators like the United States Army Corps of Engineers seek their traditional petroleum-based fluids with environmentally acceptable hydraulic fluids (EAHF) to reduce their impact and liability related to spills and leakages to the water and environment. Artesion, Inc. and its sub-contractor Washington State University (WSU) sought to optimize WSU’s existing EAHF blend into an improved product that would demonstrate long-term stability while meeting the EAHF requirements of the EPA’s Vessel General Permit (VGP). Multiple rounds of Design of Experiments testing were performed from WSU’s base formulation, modifying mixing ratios to generate multiple test fluids. These fluids were then tested for hydraulic fluid properties. It was found that there was a significant tradeoff between oxidative stability and biodegradability; highly stable materials were not sufficiently biodegradable, while the highly biodegradable materials quickly failed in stability tests. After four rounds of Design of Experiments, AI and WSU had found a base fluid which met the VGP, but only had a Rotating Pressure Vessel Oxidative Test (RPVOT) of 284-minute RPVOT stability, far short of the 500-minute target that would be needed for hydroelectric plants. It was determined that WSU’s route had shown initial promise but needed more refinement to be able to produce an acceptable EAHF

Initial mechanisms for the dissociation of carbon from electronically-excited nitrotoluene molecules

We calculated the photoinduced decomposition of various nitrotoluene molecules, resulting in the formation of atomic carbon, at the B3LYP/6-311++G(d,p) level of theory using Gaussian 09. In addition, we used TD-DFT (B3LYP/6-311++G(d, p)) to calculate the excitation energies. The results confirm our previously reported experimental results. Specifically, we show that the absorption of 226 nm (5.49 eV) light can lead to the decomposition of nitrotoluene molecules and the formation of atomic carbon. One 226 nm photon is sufficient for the dissociation of carbon from 2-NT and 4-NT molecules. During the dissociation process, the CH3 group provides the dissociated carbon atom and the NO2 group accepts the H atoms from either the CH3 group or the benzene ring before carbon exits the molecular system. For the second and third carbon dissociation of 2-NT, the energy barriers are 6.70 eV and 7.43 eV, respectively, and two 226 nm photons would need to be absorbed by the molecule. If extra NO is present during the first carbon dissociation of 2-NT, it gets involved in the last two decomposition steps and forms a C=NH-N=O structure which stabilizes the decomposition products and lowers the energy barrier from 5.22 eV to 4.70 eV. However, for the second and third carbon dissociation of 2-NT, the NO molecules have no apparent effect. For nitrotoluene molecules with two or three NO2 groups (i.e., 2,4-DNT, 2,6-DNT, 3,4-DNT, and 2,4,6-TNT), the first carbon dissociation energies are between 5.26 eV and 5.57 eV. The carbon dissociation pathways for these molecules are similar to those of 2-NT. In 2,4-DNT, the lowest energy barriers for the second and third carbon dissociation are 6.54 eV and 6.60 eV, respectively, which are about 1 eV higher than the energy barrier for the first carbon dissociation. In case of 2,4-DNT/NO and 2,4,6-TNT/NO, NO acts as a catalyst in the first carbon dissociation processes and forms a C=NH-N=O structure which lowers the energy barriers by 0.48 eV and 0.89 eV, respectively. (c) 2017 Author(s)

Modeling ex-situ thermal impulse sensor responses to non-isothermal heating profiles

Ex-situ thermal impulse sensing based on irreversible phase transitions has been a developing field over the past two decades. Typically, these techniques determine thermal impulses assuming a perfect isothermal heating profile, which is not the case for real-life temperature profiles in extreme environments (e.g., structural fires, explosions, gas turbines). To better understand how real-world temperature profiles influence the sensors thermal impulse determinations, we perform phenomenological modeling of a thermal impulse sensor’s response to non-isothermal heating with four-key profile characteristics: finite heating rate, nonzero cooling time constant, temperature spikes, and non-isothermal heating due to the finite size of sensors. We find that in all cases, these effects result in the corresponding equivalent isothermal temperature being lower than the peak temperature, while the equivalent isothermal duration is found to either be lengthened or shortened depending on the effect of interest. These results have important implications for the interpretation of thermal impulse calculations from a wide range of ex-situ thermal impulse sensors

UV AND 532 NM PHOTODISSOCIATION OF O-NITROTOLUENE: DETECTION OF ELECTRONICALLY EXCITED NITRIC OXIDE IN NITROGEN AND ARGON

Author Institution: Applied Sciences Laboratory, Institute for Shock Physics, Washington State University, Spokane, WA 99210-1495, USAIt is well known that NO is one of the main fragments produced by photodissociation of o-nitrotoluene. We detected vibrationally-excited NO in ground and electronically excited states using LIF. We also observed emission due to the formation of C(I) which is overlapping with NO emission. In the presence of N$_2$, longer lifetime of the NO emission is observed showing evidence of energy transfer from highly excited N$_2$. In the presence of Ar, evidence of o-nitrotoluene-Ar cluster formation was observed