Chemical doping of organic semiconductors is a common technique used to increase the performance numerous organic electronic and optoelectronic devices. Tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) is one of the most widely known p-dopants having the properties necessary to act as a strong electron acceptor. Despite its strong electron accepting abilities, F4-TCNQ is extremely expensive, making it less than ideal for large-area applications. Here, we introduce a small molecule called Tetracyanoindane (TCI) as a potential p-dopant. Widely known for its role in the field of non-linear optics, its high polarizability arises from the addition of four cyano-groups, which are electron withdrawing groups. The four cyano-groups are also seen in the F4-TCNQ molecule and contributes to the withdrawing strength alongside the four fluorine atoms present. We hypothesize that TCI could have similar accepting strength to F4-TCNQ and could potentially replace it as a cheaper alternative. In this study, Cyclic Voltammetry (CV), UV-Visible-Near Infrared Spectroscopy (UV/Vis/NIR), Photoluminescence (PL), Current-Voltage (IV) measurements analysis was conducted to compare the accepting strength of TCI and F4-TCNQ. Then, the two molecules were added to Poly-3-hexy-thiophene (P3HT) to observe how readily they dope the organic semiconductor.

A new class of high-temperature materials based on refractory elements was investigated with an aim to improve the energy efficiency of thermal power plants. Alloys based on Nb and Mo composed of BCC solid solution (BCCss) (Nb-Mo) and T2-silicide (Nb,Mo)5(Si,B)3 are promising candidates as high-temperature materials. Further investigation on the alloy phase equilibria of this system is required to improve the mechanical properties and oxidation resistance through optimization of the phase compositions. Cr is one candidate to modify the properties of the alloy because Cr is expected to stabilize the T2 compound phase along with B. Here, the phase equilibria among BCCss and the T2 compound are widely investigated in the Cr-Mo-Nb-Si-B system, and a BCCss-T2 two-phase microstructure is found in Mo-rich alloys. The B/Si ratio in the T2 phase increases with the Cr content, while almost no B solubility was found in BCCss. As the Si content increases in alloys, the A15 silicide phase ((Cr, Mo, Nb)3Si) and/or Laves phase appear.

Nanoindentation tests were conducted to investigate the mechanical properties of the BCCss phase of the alloys in the Cr-Mo-Nb-Si-B system. The nanohardness and reduced elastic modulus of these alloys tended to be higher with an increase in Cr.

An alternative method for the standardless quantitative x-ray diffraction analysis of mixtures of inorganic crystalline phases proposed in the literature several years ago is presented. Our method requires only previously calculated μ*i values from tabulated data for all phases present in the mixtures. It does not require either the determination of calibration constants or the use of external standards, but it does require that the number of analyzed mixtures is larger than or equal to the number of phases present in them, and that the chemical composition of the mixtures are significantly different from each other. The integrated intensities of the chemically pure phases are estimated by a least-squares procedure from XRD data obtained from the mixtures. The method was tested against data published in the literature, with good results. Finally, a general expression for the “Normalized Height Law” proposed on an empirical basis by other researchers, has been theoretically derived.

Chitosan (Ch)-Polyvinyl (alcohol) (PVA) hydrogels cross-linked with sodium tripolyphosphate were synthetized to obtain a polymer matrix encapsulating an insecticide (active ingredient: imidacloprid). Imidacloprid release tests were performed separately with moist and lyophilized hydrogel beads with a diameter of 3.47 and 3.30 mm respectively. The concentration of the insecticide released in the medium was determined by UV-Visible spectroscopy, reaching equilibrium for wet hydrogels at 72h at a concentration of 330 mg L-1 and 281 mg L-1 in 48h for lyophilized hydrogels, comparing it with a maximum load of 330.18 mg L-1of imidacloprid contained in the hydrogels. The characterization of hydrogels was performed by Fourier transform infrarred spectroscopy (FTIR) to determine the functional groups. The morphology of the polymer matrix of the hydrogels was carried out in a scanning electron microscope (SEM). The size distribution and diameter of bead samples were observed through a stereomicroscope. The percentage of humidity of the hydrogels was determined obtaining 94.8% once the imidacloprid was released. the pore size of the samples was determined by the Brunauer-Emmet-Teller (BET) technique. The techniques used indicated that controlled release of imidacloprid could be more efficient with wet hydrogels in relation to the maximum load of imidacloprid contained, for protection of crops is necessary for a long time because of insecticide disponible in the soil.

Glassy carbon nanolattices can exhibit very high strength-to-weight ratios as a consequence of their small size and the material properties of the constituent material. Such nanolattices can be fabricated by pyrolysis of polymeric microlattices. To further elucidate the influence of the mechanical size effect of the constituent material, compression tests of glassy carbon nanopillars with varying sizes were performed. Depending on the specific initial polymer material and the nanopillar size, varying mechanical properties were observed. Small nanopillars exhibited elastic-plastic deformation before failure initiation. Moreover, for smaller nanopillars higher strength values were observed than for larger ones, which might be related to smaller defects and a lower defect concentration in the material.

We visually observed color changes of discontinuous gold surfaces on paper substrates through localized surface plasmon resonance (LSPR) at room temperature due to surface diffusion of gold nanostructures. Isolated nanoparticles and an uncompleted nanosheet of gold were obtained by thermal vapor deposition. After preservation for 8 months in air at room temperature, the particle sizes and shapes remarkably changed with color changes. The surface diffusion of the discontinuous gold on the paper would be derived from solid-state dieting, resulting in the growth of the nanosheet defect and coalescence of the nanoparticles. This is due to the total energy minimization of the surfaces of gold nanostructures and the paper and the interface between gold and the paper.

Our preliminary investigation of the absorption and the photoluminescence response of selectively separated graphene quantum dots using centrifugation indicate that the photoluminescence is more sensitive to the size of the quantum dot than the absorption. We observed ∼143nm blueshift from 623nm to 480nm in the visible region of the photoluminescence with increasing successive centrifugation (decreasing size) and not in the corresponding absorption spectra in the visible region. However, for the first time, we observed a blueshift in the absorption spectra in the UV regions that is tentatively attributed to quantum confinement. Further detailed work is underway to confirm the blueshift in the absorption and correlate with deep UV photoluminescence and morphological quantification of the quantum dots size distribution using high resolution transmission electron microscope.

There is growing evidence that minimizing the mechanical mismatch between neural implants and brain tissue mitigates inflammatory, biological responses at the interface under long-term implant conditions. The goal of this study is to develop a brain-like soft, conductive neural interface and use an improvised, penetrating microindentation technique reported by us earlier to quantitatively assess the (a) elastic modulus of the neural interface after implantation, (b) mechanical stresses during penetration of the probe, and (c) periodic stresses at steady-state due to tissue micromotion around the probe. We fabricated poly- dimethylsiloxane (PDMS) matrices with multi-walled carbon nanotubes (MWCNTs) using two distinct but carefully calibrated cross-linking ratios, resulting in hard (elastic modulus∼484 kPa) or soft, brain-like (elastic modulus∼5.7 kPa) matrices, the latter being at least 2 orders of magnitude softer than soft neural interfaces reported so far. Subsequent loading of the hard and soft silicone based matrices with (100% w/w) low-molecular weight PDMS siloxanes resulted in further decrease in the elastic modulus of both matrices. Carbon probes with soft PDMS coating show significantly less maximum axial forces (-587 ± 51.5 µN) imposed on the brain than hard PDMS coated probes (-1,253 ± 252 µN) during and after insertion. Steady-state, physiological micromotion related stresses were also significantly less for soft- PDMS coated probes (55.5 ± 17.4 Pa) compared to hard-PDMS coated probes (141.0 ± 21.7 Pa). The penetrating microindentation technique is valuable to quantitatively assess the mechanical properties of neural interfaces in both acute and chronic conditions.

Nuclear wastes generated from reprocessing of used nuclear fuel tend to contain a large fraction of rare earth (RE, e.g., Nd3+), transition (TM, e.g., Mo6+, Zr4+), alkali (A, e.g., Cs+), and alkaline earth cations (AE, e.g., Ba2+, Sr2+). Various strategies have been considered for immobilizing such waste streams, varying from nominally crystal-free glass to glass-ceramic to multi-phase ceramic waste forms. For glass and glass-ceramic waste forms, the added glass-forming system is generally alkali-alkaline earth-aluminoborosilicate (i.e., Na-Ca-Al-B-Si oxide). In a US-UK collaborative project, summarized here, we investigated the glass structure and crystallization dependence on compositional changes in simulated nuclear waste glasses and glass-ceramics. Compositions ranged in complexity from five – to – eight oxides. Specifically, the roles of Mo and rare earths are investigated, since a proposed glass-ceramic waste form contains crystalline phases such as powellite [(AE,A,RE)MoO4] and oxyapatite [(RE,AE,A)10Si6O26], and the precipitation of molybdenum phases is known to be affected by the rare earth concentration in the glass. Additionally, the effects of other chemical additions have been systematically investigated, including Zr, Ru, P, and Ti. A series of studies were also undertaken to ascertain the effect of the RE size on glass structure and on partitioning to crystal phases, investigating similarities and differences in glasses containing single RE oxides of Sc, Y, La, Ce, Nd, Sm, Er, Yb, or Lu. Finally, the effect of charge compensation was investigated by considering not only the commonly assessed peralkaline glass but also metaluminous and peraluminous compositions. Glass structure and crystallization studies were conducted by spectroscopic methods (i.e., Raman, X-ray absorption, nuclear magnetic resonance (NMR), optical absorption, photoluminescence, photoluminescence excitation, X-ray photoelectron spectroscopy), microscopy (i.e., scanning electron microscopy, transmission electron microscopy, electron probe microanalysis), scattering (i.e., X-ray and neutron diffraction, small angle measurements), and physical characterization (i.e., differential thermal analysis, liquidus, viscosity, density). This paper will give an overview of the research program and some example unpublished results on glass-ceramic crystallization kinetics, microstructure, and Raman spectra, as well as some examples of the effects of rare earths on the absorption, luminescence, and NMR spectra of starting glasses. The formal collaboration described here has resulted in the generation of a large number of results, some of which are still in the process of being published as separate studies.

Plasmonic metallic nanoparticles can significantly enhance the catalytic efficiency of semiconductors via plasmonic photocatalysis. In this study, a hybrid Ag/TiO2 photocatalyst was synthesized and tested for the photochemical reduction of bicarbonate to value-added formic acid. It was found that under solar irradiation, TiO2 is not very efficient, but formate production is significantly increased with the addition of silver nanoparticles. Under 365 nm irradiation, the photocatalytic efficiency of TiO2 is enhanced, but no effect was observed with the addition of silver nanoparticles. Under solar irradiation, Ag/TiO2 reached an apparent quantum efficiency (AQE) of 7.78 ± 0.04%, the highest AQE observed so far. Enhanced photocatalytic activity is attributed to the synergistic effect between UV photon excitation of TiO2 and surface plasmon resonance enhancement. To elucidate the mechanism of plasmon-enhanced photocatalysis, experiments were performed under solar irradiation and 365 nm irradiation. We propose that photo-excited electrons are transferred from above the Fermi level of the metal nanoparticle to the conduction band of the semiconductor through plasmon-induced electron transfer.