Glow discharge techniques in the chemical analysis of photovoltaic materials

The presented study gives an integrated overview on the prospects of glow discharge (GD) methods in the chemical analysis of photovoltaic materials. With a focus on recent research and important photovoltaic (PV) materials, the GD coupled analytical methods, high resolution mass spectrometry (MS), time‐of‐flight‐mass spectrometry (TOF‐MS) and optical emission spectrometry (OES) are discussed. Each exemplary study carried out will point out the most suitable GD technique for the problem at hand, at the same time showing ways to increase analytical accuracy and to overcome typical instrumental restrictions. Challenging GD‐MS analyses of thin and ultra thin films (down to 20 nm) as well as GD‐MS and GD‐OES studies of ready‐to‐use modules were carried out, showing the reader the application potential of GD methods in a PV development or production process. For the first time, novel cell concepts based on crystalline silicon on glass and silicon nanowires are analyzed by GD‐OES, revealing precise chemical information on the devices. Copyright © 2012 John Wiley & Sons, Ltd.     

Heat degradation studies of solar heat transfer fluids

Destructive distillation of solar heat transfer fluids was conducted to determine the types of pyrolytic products which might be formed in solar collectors under conditions of stagnation or malfunction. The distillates were analyzed by gas chromatography/mass spectrometry (GC/MS) to determine the types of compounds which were present and the minor components which might be formed. Dehydration products were formed from ethylene and propylene glycols with ethylene oxide and propylene oxide being minor products. A high aromatic petroleum heat transfer fluid yielded distillation fractions enriched in quinolines or isoquinolines and methylated derivatives thereof. Fractionation of this aromatic heat transfer fluid showed that the basic fraction of unheated fluid also contained aza-arenes which exhibited mutagenic activity in the Ames' bioassay. GC/MS showed that the basic fraction from unheated heat transfer fluid also contained benzoquinolines which appeared to be lacking in heat degraded samples of the same fluid. Fractionation of heat transfer fluids, in particular petroleum-based fluids, may often be necessary in order to concentrate minor components so that they can be identified by GC/MS and in order to detect mutagenic activities without interference from cytotoxic components.     

Volume and Enthalpy Changes upon Photoexcitation of Bovine Rhodopsin Derived from Optoacoustic Studies by Using an Equilibrium between Bathorhodopsin and Blue-Shifted Intermediate

A complex multistep model including an equilibrium was used for the first time to analyze data obtained by laser-induced optoacoustic spectroscopy (LIOAS) with bovine rhodopsin in washed membranes (T = 5–32°C). The thermal equilibrium was between bathorhodopsin, batho, and the blue-shifted intermediate (BSI), i.e., batho ⇄ BSI. This analysis considers a 14-ns intermediate detected by LIOAS at 25°C (with similar decay activation parameters as those reported for BSI in solubilized rhodopsin). The energy content of lumirhodopsin (lumi) and the structural volume difference between lumi and rhodopsin were essentially the same (E_lumi. = 80 kJ/mol and ΔV_lumi–rho = 40 mL/mol) for both a model based on a simple batho → BSI → lumi sequence and one including the batho ⇄; BSI equilibrium. However, the structural volume changes for the individual steps batho → BSI and BSI → lumi were markedly changed by the introduction of the equilibrium. With the rate constant for the forward reaction batho → BSI for solubilized rhodopsin determined by Hug et al. (Hug, S.J.; Lewis, W.J.; Einterz, C.M.; Thorgeirsson, T.E.; Kliger, D.S. Biochemistry, 1990 , 29, 1475–1485) the structural volume changes obtained with the equilibrium model are ΔV_BSI-batho = 79 mL/mol and ΔV_lumi-BSI = −44 mL/mol. The resulting batho → BSI expansion is larger than with the sequential model, and ΔV_lumi-BSI is now a contraction instead of an expansion. A small expansion of 5 mL/mol is derived for the formation of batho with both models. The estimated energy content of BSI is clearly higher than the value of lumi. The structural volume changes between batho, BSI, and lumi derived from the equilibrium model correlate better than those from the simple sequential model with the chromophore transition dipole moment changes determined in the literature using linear dichroism measurements. The structural volume changes are discussed in terms of the variations upon transformation of the chromophore–protein interactions.     

Hydrogen-Bond Dynamics and Solvation of Electronically Excited States as Determined by Femtosecond Vibrational Spectroscopy

The ultrafast dynamics of site-specific hydrogen bonds between an organic chromophore serving as hydrogen acceptor and a hydrogen-donating species in solution is studied by femtosecond vibrational spectroscopy. This new method gives specific insight into microscopic structural changes of hydrogen bonds initiated by electronic excitation of the chromophore. We study H-bonded complexes of coumarin 102 with the solvent CHCl₃, and with phenol. Upon electronic excitation, the intermolecular hydrogen bond between proton donor and acceptor is cleaved within 200 fs, followed by a slower reorientation dynamics of the donor molecules extending into the picosecond regime. For CHCl₃, this slower rearrangement is interpreted in terms of polar solvation. In complexes consisting of a coumarin molecule and two phenol moieties, the slower dynamics is related to geometry changes of the phenol–phenol hydrogen bond. The consequences of those results for a microscopic picture of polar solvation are discussed.     

An Electrophysiological Comparison of Voltage-Gated Proton Channels,Other Ion Channels,and Other Proton Channels

Voltage-gated proton selective channels occupy an ill-defined region between “normal” ion channels and a variety of proton-conducting pathways inside proteins, including, but not limited to, membrane-bound proteins. Voltage-gated H⁺ channels closely resemble other voltage-gated ion channels in their voltage- and time-dependent gating, but differ in their extreme selectivity, their miniscule single-channel conductance, and the high activation enthalpy for conduction. Furthermore, in contrast with the “multiple occupancy” hypothesized to account for aspects of permeation through other ion channels, it seems unlikely that H⁺ channels can be occupied by more than one proton at a time. Voltage-gated H⁺ channels functionally resemble other proton-conducting pathways in proteins, but until their structure has been determined, this similarity will remain speculative. The present restriction to functional measurements is less of a handicap than might be expected—the history of ion channel research shows that deductions based on electrophysiological measurements often closely predict the eventually determined structure. Existing evidence supports the idea that protons permeate the membrane through voltage-gated H⁺ channels by hopping across a hydrogen-bonded chain that consists of at least some amino acid side groups in addition to water molecules.     

Analysis of Aerosols from the World Trade Center Collapse Site,New York,October 2 to October 30, 2001

The collapse of the World Trade Center (WTC) buildings #2 (South Tower), #1 (North Tower), and #7 created an enormous collapse pile which emitted intense plumes of acrid smoke and dust until roughly mid-December, when the last spontaneous surface fire occurred. We collected particles by size (8 modes, ≈12 to 0.09 micrometers diameter) and time (typical resolution of 1 to 3 h) from October 2 until late December at the EML 201 Varick Street site roughly 1.8 km NNE of the collapse site and 50 m above ground level. Here we show some of the 70,000 mass and elemental data from the time period October 2 through October 30. Identification of a WTC collapse pile source for aerosols seen at the receptor site were based upon the simultaneous presence of finely powdered concrete, gypsum, and glass with intense very fine combustion mode mass episodes concurrent with winds from the southwest quadrant. The results, derived from seven independent beam-based analytical techniques, showed that while PM₁₀ and PM_2.5 24 h values rarely, if ever, violated federal air quality standards, WTC-derived plumes swept over lower Manhattan Island, resulting in intense aerosol impacts of duration a few hours at any one site. The WTC plume resembled in many ways those seen from municipal waste incinerators and high temperatures processes in coal-fired power plants. The size fractions above 1 micrometer contained finely powdered concrete, gypsum, and glass, with sootlike coatings and anthropogenic metals, but little asbestos. Composition in the very fine size range (0.26 > D_p > 0.09 μm) was dominated by sulfuric acid and organic matter, including polycyclic aromatic hydrocarbons (PAHs) and their derivatives, and glasslike silicon-containing aerosols. Many metals were seen in this mode, most, but not all, at low concentrations. The concentrations of very fine silicon, sulfur, and many metals, as well as coarse anthropogenic metals, decreased markedly during October, probably in association with the cooling of the collapse piles. Values of very fine elements seen in May, 2002 at the WTC site were only a few percent of October values.     

Size Distributions of Species in Fine Particles in Denver Using a Microorifice Impactor

Size-fractionated fine particles in Denver, Colorado, were collected by a microorifice impactor and analyzed for mass and elemental composition by a β-gauge and an X-ray fluorescence spectrometer. A least-squares procedure was used to fit a lognormal distribution function to the data in order to determine values and uncertainties for the mass median aerodynamic diameter and geometric standard deviation. The validity of the uncertainties so determined was tested by comparing them to uncertainties derived from Monte Carlo simulations.