Advanced Analytical Microscopy at the Nanoscale: Applications in Wide Bandgap and Solid Oxide Fuel Cell Materials

The atomic-level structure and chemistry of materials ultimately dictate their observed macroscopic properties and behavior. As such, an intimate understanding of these characteristics allows for better materials engineering and improvements in the resulting devices. In our work, two material systems were investigated using advanced electron and ion microscopy techniques, relating the measured nanoscale traits to overall device performance. First, transmission electron microscopy and electron energy loss spectroscopy (TEM-EELS) were used to analyze interfacial states at the semiconductor/oxide interface in wide bandgap SiC microelectronics. This interface contains defects that significantly diminish SiC device performance, and their fundamental nature remains generally unresolved. The impacts of various microfabrication techniques were explored, examining both current commercial and next-generation processing strategies. In further investigations, machine learning techniques were applied to the EELS data, revealing previously hidden Si, C, and O bonding states at the interface, which help explain the origins of mobility enhancement in SiC devices. Finally, the impacts of SiC bias temperature stressing on the interfacial region were explored. In the second system, focused ion beam/scanning electron microscopy (FIB/SEM) was used to reconstruct 3D models of solid oxide fuel cell (SOFC) cathodes. Since the specific degradation mechanisms of SOFC cathodes are poorly understood, FIB/SEM and TEM were used to analyze and quantify changes in the microstructure during performance degradation. Novel strategies for microstructure calculation from FIB-nanotomography data were developed and applied to LSM-YSZ and LSCF-GDC composite cathodes, aged with environmental contaminants to promote degradation. In LSM-YSZ, migration of both La and Mn cations to the grain boundaries of YSZ was observed using TEM-EELS. Few substantial changes however, were observed in the overall microstructure of the cells, correlating with a lack of performance degradation induced by the H2O. Using similar strategies, a series of LSCF-GDC cathodes were analyzed, aged in H2O, CO2, and Cr-vapor environments. FIB/SEM observation revealed considerable formation of secondary phases within these cathodes, and quantifiable modifications of the microstructure. In particular, Cr-poisoning was observed to cause substantial byproduct formation, which was correlated with drastic reductions in cell performance.

CHARACTERIZATION OF THERMAL AND MECHANICAL PROPERTIES OF POLYPROPYLENE–BASED COMPOSITES FOR FUEL CELL BIPOLAR PLATES AND DEVELOPMENT OF EDUCATIONAL TOOLS IN HYDROGEN AND FUEL CELL TECHNOLOGIES

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Boosting microbial fuel cell performance by combining with an external supercapacitor

Microbial Fuel Cells (MFC) technology finds space as a promising technology as a green alternative power-generating device, by the possibility to convert organic matter directly into electricity by microbially catalysed reactions, especially for the potential of the simultaneous treatment of wastewaters. Despite the studies that were carried out over the decades, MFCs still provide insufficient power and current densities in order to be commercially attractive in the energy market. Scientific community today pursues two main strategies in order to increase the overall performance output of the MFC. The first is to support the cells with an external supercapacitor (SC), which is able to accept and deliver charge much faster than normal capacitors, thanks to the use of an electrostatic double-layer capacitance, in combination with pseudocapacitance. The second is to implement directly the SC into the MFC, by using carbon electrodes with high surface area, similar to the SC. Both strategies are eventually supported by the use of charge boosters, respect to the application of the MFC. Galvanostatic measures for the MFC and SCs are performed at different currents, alone and by integration of both devices. The SCs used have a capacitance respectively of 1F, 3F and 6F. Subsequently, a stack of MFCs is assembled and paired to a 3F SC, in order to power an ambient diffuser, able to spray at intervals with a can and a controller. In conclusion, the use of a SC in parallel to the MFCs increases the overall performance of the system. The SC remove the discharge current limit of the MFC and increases the energy and power delivered by the system, allowing it to power for a certain time the ambient diffuser successfully. The key factor highlighted by the final experiment was the insufficient charging time of the SC, resulting finally in a voltage that is inadequate to power the device. Further studies are therefore necessary to improve the performance of the MFCs.

Effect of temperature on the electro-oxidation of ethanol on platinum

We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC) in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, and anions. The formation of oxygenated species at high potentials, mainly in the more diluted electrolyte, also contributes to increase the electro-oxidation reaction rate.

Electrochemical Evidence of Strong Electronic Interaction of PtRu on Carbon Nanotubes with High Density of Defects

We show that carbon nanotubes (CNTs) with high density of defects can present a strong electronic interaction with nanoparticles of Pt-Ru with average particle size of 3.5 +/- 0.8 nm. Depending on the Pt-Ru loading on the CNTs, CO and methanol oxidation reactions suggest there is a charge transfer between Pt-Ru that in turn provokes a decrease in the electronic interaction taking place between Ru and Pt in the PtRu alloy. The CO stripping potentials were observed at about 0.65 and 0.5 V for Pt-Ru/CNT electrodes with Pt-Ru loadings of 10 and 20, and 30 wt %, respectively. (C) 2008 The Electrochemical Society. [DOI: 10.1149/1.2990222] All rights reserved.

Gold is not a Faradaic-Efficient Borohydride Oxidation Electrocatalyst: An Online Electrochemical Mass Spectrometry Study

Direct borohydride fuel cells are promising high energy density portable generators. However, their development remains limited by the complexity of the anodic reaction: The borohydride oxidation reaction (BOR) kinetics is slow and occurs at high overvoltages, while it may compete with the heterogeneous hydrolysis of BH(4)(-). Nevertheless, one usually admits that gold is rather inactive toward the heterogeneous hydrolysis of BH(4)(-) and presents some activity regarding the BOR, therefore yielding to the complete eight-electron BOR. In the present paper, by coupling online mass spectrometry to electrochemistry, we in situ monitored the H(2) yield during BOR experiments on sputtered gold electrodes. Our results show non-negligible H(2) generation on Au on the whole BOR potential range (0-0.8 V vs reversible hydrogen electrode), thus revealing that gold cannot be considered as a faradaic-efficient BOR electrocatalyst. We further propose a relevant reaction pathway for the BOR on gold that accounts for these findings.

In situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction

Early reports stated that Au was a catalyst of choice for the BOR because it would yield a near complete faradaic efficiency. However, it has recently been suggested that gold could yield to some extent the heterogeneous hydrolysis of BH(4)(-),therefore lowering the electron count per BH(4)(-), especially at low potential. Actually, the blur will exist regarding the BOR mechanism on Au as long as no physical proof regarding the reaction intermediates is not put forward. In that frame, in situ physical techniques like FTIR exhibit some interest to study the BOR. Consequently, in situ infrared reflectance spectroscopy measurements (SPAIRS technique) have been performed in 1 M NaOH/1 M NaBH(4) on a gold electrode with the aim to detect the intermediate species. We monitored several bands in B-H ((nu) over bar similar to 1180,1080 and 972 cm(-1)) and B-O bond regions ((nu) over bar =1325 and similar to 1425cm(-1)), which appear sequentially as a function of the electrode polarization. These absorption bands are assigned to BH(3), BH(2) and BO(2)(-) species. At the light of the experimental results, possible initial elementary steps of the BOR on gold electrode have been proposed and discussed according to the relevant literature data.

Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen

Physical and electrochemical properties of nanostructured Ni-doped manganese oxides (MnO(x)) catalysts supported on different carbon powder substrates were investigated so as to characterize any carbon substrate effect toward the oxygen reduction reaction (ORR) kinetics in alkaline medium. These NiMnO(x)/C materials were characterized using physicochemical analyses. Small insertion of Ni atoms in the MnO(x) lattice was observed, which consists of a true doping of the manganese oxide phase. The corresponding NiMnO(x) phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm (from x-ray diffraction analyses). Layered manganite (MnOOH) phase has been detected for the Monarch 1000-supported NiMnO(x) material, while different species of MnO(x) phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnO(x) catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnO(x)/C catalysts, with the occurrence of minority HO(2)(-) disproportionation reaction. The HO(2)(-) disproportionation reaction progressively increases with the Ni content in NiMnO(x) materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3528439] All rights reserved.

Extracellular alkalinization induces endothelium-derived nitric oxide dependent relaxation in rat thoracic aorta

Aim: To investigate the mechanism through which the extracellular alkalinization promotes relaxation in rat thoracic aorta. Methods: The relaxation response to NaOH-induced extracellular alkalinization (7.4-8.5) was measured in aortic rings pre-contracted with phenylephrine (Phe, 10(-6) M). The vascular reactivity experiments were performed in endothelium-intact and -denuded rings, in the presence or and absence of indomethacin (10(-5) M), NG-nitro-L-arginine methyl ester (L-NAME, 10(-4) M), N-(6-Aminohexyl)-5-chloro-1-naphthalenesulfonamide/HCl (W-7, 10(-7) M), 2,5-dimethylbenzimidazole (DMB, 2 x 10(-5) M) and methyl-B-cyclodextrin (10(-2) M). In addition, the effects of NaOH-induced extracellular alkalinization (pH 8.0 and 8.5) on the intracellular nitric oxide (NO) concentration was evaluated in isolated endothelial cells loaded with diaminofluorescein-FM diacetate (DAF-FM DA, 5 mu M), in the presence and absence of DMB (2 x 10(-5) M). Results: The extracellular alkalinization failed to induce any change in vascular tone in aortic rings pre-contracted with KCl. In rings pre-contracted with Phe, the extracellular alkalinization caused relaxation in the endothelium-intact rings only, and this relaxation was maintained after cyclooxygenase inhibition; completely abolished by the inhibition of nitric oxide synthase (NOS), Ca(2+)/calmodulin and Na(+)/Ca(2+). exchanger (NCX), and partially blunted by the caveolae disassembly. Conclusions: These results suggest that, in rat thoracic aorta, that extracellular alkalinization with NaOH activates the NCX reverse mode of endothelial cells in rat thoracic aorta, thereby the intracellular Ca(2+) concentration and activating the Ca(2+)/calmodulin-dependent NOS. In turn, NO is released promoting relaxation. (C) 2010 Elsevier Inc. All rights reserved.

Photodynamic Inactivation of Conidia of the Fungi Metarhizium anisopliae and Aspergillus nidulans with Methylene Blue and Toluidine Blue

Antimicrobial photodynamic treatment (PDT) is a promising method that can be used to control localized mycoses or kill fungi in the environment. A major objective of the current study was to compare the conidial photosensitization of two fungal species (Metarhizium anisopliae and Aspergillus nidulans) with methylene blue (MB) and toluidine blue (TBO) under different incubation and light conditions. Parameters examined were media, photosensitizer (PS) concentration and light source. PDT with MB and TBO resulted in an incomplete inactivation of the conidia of both fungal species. Conidial inactivation reached up to 99.7%, but none of the treatments was sufficient to achieve a 100% fungicidal effect using either MB or TBO. PDT delayed the germination of the surviving conidia. Washing the conidia to remove unbound PS before light exposure drastically reduced the photosensitization of A. nidulans. The reduction was much smaller in M. anisopliae conidia, indicating that the conidia of the two species interact differently with MB and TBO. Conidia of green and yellow M. anisopliae mutants were less affected by PDT than mutants with white and violet conidia. In contrast to what occurred in PBS, photosensitization of M. anisopliae and A. nidulans conidia was not observed when PDT was performed in potato dextrose media.

Activity of platinum-tin catalysts prepared by the Pechini-Adams method for the electrooxidation of ethanol

Pt-Sn electrocatalysts of different compositions were prepared and dispersed on carbon Vulcan XC-72 using the Pechini-Adams method. The catalysts were characterized by energy dispersive X-ray analysis and X-ray diffraction. The electrochemical properties of these electrode materials were also examined by cyclic voltammetry and chronoamperometric experiments in acid medium. The results showed that the presence of Sn greatly enhances the activity of Pt towards the electrooxidation of ethanol. Moreover, it contributes to reduce the amount of noble metal in the anode of direct alcohol fuel cells, which remains one of the challenges to make the technology of direct alcohol fuel cells possible. Electrolysis of ethanol solutions at 0.55 V vs. RHE allowed to determine by liquid chromatography acetaldehyde and acetic acid as the main reaction products. CO(2) was also analyzed after trapping it in a NaOH solution indicating that the cleavage of the C-C bond in the ethanol molecule did occur during the adsorption process. In situ IR reflectance spectroscopy helped to investigate in more details the reaction mechanism through the identification of the reaction products as well as the presence of some intermediate adsorbed species, such as linearly bonded carbon monoxide. (C) 2009 Elsevier B.V. All rights reserved.

Laminin 10/11: an alternative adhesive ligand for epidermal keratinocytes with a functional role in promoting proliferation and migration

We have investigated the expression and function of the isoforms of laminin bearing the alpha(5) chain, i.e. laminin-10/11 in neonatal and adult human skin. By immunostaining human skin derived from a variety of anatomic sites, we found that the laminin-alpha(5) chain is expressed abundantly in the basement membrane underlying the interfollicular epidermis and the blood vessels in the dermis. Interestingly, while the expression level of the well-studied laminin-5 isoform did not change significantly with age, laminin-10/11 (a5 chain) appeared to decrease in the basement membrane underlying the epidermis, in adult skin. In contrast, the levels of laminin-10/11 in the basement membrane underlying blood vessels remained unchanged in neonatal vs. adult skin. Importantly, in vitro cell adhesion assays demonstrated that laminin-10/11 is a potent adhesive substrate for both neonatal and adult keratinocytes and that this adhesion is mediated by the alpha(3)beta(1), and alpha(6)beta(4) integrins. Adhesion assays performed with fractionated basal keratinocytes showed that stem cells, transit amplifying cells and early differentiating cells all adhere to purified laminin-10/11 via these receptors. Further, laminin-10/11 provided a proliferative signal for neonatal foreskin keratinocytes, adult breast skin keratinocytes, and even a human papillomavirus type-18 transformed tumorigenic keratinocyte cell line in vitro. Finally, laminin-10/11 was shown to stimulate keratinocyte migration in an in vitro wound healing assay. These results provide strong evidence for a functional role for laminin-10/11 in epidermal proliferation during homeostasis, wound healing and neoplasia.

Field quantization, photons and non-Hermitean modes

Field quantization in unstable optical systems is treated by expanding the vector potential in terms of non-Hermitean (Fox-Li) modes. We define non-Hermitean modes and their adjoints in both the cavity and external regions and make use of the important bi-orthogonality relationships that exist within each mode set. We employ a standard canonical quantization procedure involving the introduction of generalized coordinates and momenta for the electromagnetic (EM) field. Three-dimensional systems are treated, making use of the paraxial and monochromaticity approximations for the cavity non-Hermitean modes. We show that the quantum EM field is equivalent to a set of quantum harmonic oscillators (QHOs), associated with either the cavity or the external region non-Hermitean modes, and thus confirming the validity of the photon model in unstable optical systems. Unlike in the conventional (Hermitean mode) case, the annihilation and creation operators we define for each QHO are not Hermitean adjoints. It is shown that the quantum Hamiltonian for the EM field is the sum of non-commuting cavity and external region contributions, each of which can be expressed as a sum of independent QHO Hamiltonians for each non-Hermitean mode, except that the external field Hamiltonian also includes a coupling term responsible for external non-Hermitean mode photon exchange processes. The non-commutativity of certain cavity and external region annihilation and creation operators is associated with cavity energy gain and loss processes, and may be described in terms of surface integrals involving cavity and external region non-Hermitean mode functions on the cavity-external region boundary. Using the essential states approach and the rotating wave approximation, our results are applied to the spontaneous decay of a two-level atom inside an unstable cavity. We find that atomic transitions leading to cavity non-Hermitean mode photon absorption are associated with a different coupling constant to that for transitions leading to photon emission, a feature consequent on the use of non-Hermitean mode functions. We show that under certain conditions the spontaneous decay rate is enhanced by the Petermann factor.

Extensive vascularization of developing mouse ovaries revealed by caveolin-1 expression

Expression screening for genes preferentially expressed in mouse fetal ovaries relative to testes identified Cav-1 as a candidate female-specific gene. Cav-1 encodes caveolin-1, a component of the cell membrane invaginations known as caveolae, which are involved in lipid regulation and signal transduction. In situ hybridization revealed high levels of Cav-1 mRNA in developing ovaries, compared with moderate or low levels in testes. Analysis of caveolin-1 protein distribution by immunofluorescence showed this difference to be due to the development of a dense and complex vascular network in the developing ovary. These observations point to a higher degree of differentiation and organization of the early stage mammalian ovary than previously suspected. (C) 2002 Wiley-Liss, Inc.