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At least 91 records · Page 5

Photothermal degradation of ethylene/vinylacetate copolymer

Photothermal degradation studies were conducted on a 'stabilized' formulation of ethylene/vinyl acetate copolymer (EVA) in the temperature range 25-105 C under three different oxygen environments (in open air, with limited access to O2, and in a dark closed stagnant oven). These studies were performed in order to evaluate the utility of EVA as an encapsulation material for photovoltaic modules. Results showed that at low temperature (25 C), slow photooxidation of the polymer occurred via electronic energy transfer involving the UV absorber incorporated in the polymer. However, no changes in the physical properties of the bulk polymer were detected up to 1500 hours of irradiation. At elevated temperatures, leaching and evaporation of the additives occurred, which ultimately resulted in the chemical crosslinking of the copolymer and the formation of volatile photoproducts such as acetic acid.

Liang, R. H.↗

Polymers in solar energy utilization

A laser photoacoustic technique (LPAT) has been verified for performing accelerated life testing of outdoor photooxidation of polymeric materials used in solar energy applications. Samples of the material under test are placed in a chamber with a sensitive microphone, then exposed to chopped laser radiation. The sample absorbs the light and converts it to heat by a nonradiative deexcitation process, thereby reducing pressure fluctuations within the cell. The acoustic signal detected by the microphone is directly proportional to the amount of light absorbed by the specimen. Tests were performed with samples of ethylene/methylacrylate copolymer (EMA) reprecipitated from hot cyclohexane, compressed, and molded into thin (25-50 microns) films. The films were exposed outdoors and sampled by LPAT weekly. The linearity of the light absorbed with respect to the acoustic signal was verified.Correlations were established between the photoacoustic behavior of the materials aged outdoors and the same kinds of samples cooled and heated in a controlled environment reactor. The reactor tests were validated for predicting outdoor exosures up to 55 days.

Liang, R. H.↗

Photochemical stability of UV-screening transparent acrylic copolymers of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole

The mechanism of photodegradation of certain hydroxyphenyl benzotriazole based ultraviolet absorbers has been investigated and a new polymerizable ultraviolet absorber in this group has been synthesized. The photoreactivity is entirely confined at the surface of polymethylmethacrylate films containing the ultraviolet absorbers as pendant groups. A mechanism involving sensitized photooxidation has been proposed to interpret the data.

Gupta, A.↗

Laser Photoacoustic Technique Detects Photo-Oxidation

Laser photoacoustic instrument detects small amounts of oxidation in polymers. Instrument used to evaluate resistance to oxidation in Sunlight of polymer encapsulants for solar-cell arrays. With instrument, researchers monitor samples for early stages of photooxidation and study primary mechanisms of oxidation and degradation. Effects of these mechanisms masked during later stages.

Liange, R. H.↗

Stabilized unsaturated polyesters

An unsaturated polyester, such as propylene glycolmaleic acid phthalic acid prepolymer dissolved in styrene is interpolymerized with an ultraviolet absorber and/or an antioxidant. The unsaturated chain may be filled with H or lower alkyl such as methyl and tertiary alkyl such as tertiary butyl. A polymer stable to exposure to the outdoors without degradation by ultraviolet radiation, thermal and/or photooxidation is formed.

Vogl, O.↗

Photothermal degradation studies

Key reaction intermediates of photooxidation identified and characterized by laser flash Electron Spin Resonance (ESR) spectroscopy were discussed. Effects of temperature and ultraviolet intensity were studied in order to develop meaningful accelerated testing procedures for encapsulant evaluation. In a program to study the failure of Tedlar/ethylene vinyl acetate (EVA)/stainless steel modules, failure modes similar to those observed outdoors in real-time conditions were simulated in accelerated testing. An experimental technique was developed to quantitatively assess the extent of degradation.

Liang, R. H.↗

Atmospheric CH4, CO and OH from 1860 to 1985

Studies have shown that atmospheric methane, CO and the gaseous OH radical are interdependent: if CH4, CO or OH is perturbed, background concentrations of the other two constituents are affected. Perturbations to OH alter photooxidation rates of numerous natural and anthropogenic trace gases and affect lifetimes of those species that pass from the earth's surface to the free troposphere and stratosphere. It is now known that global atmospheric methane concentrations are increasing; less definite data suggest that carbon monoxide is also increasing. Even before the measurements reported in nine literature references, modeling studies of CH4-CO-OH coupling had led to predictions (Chameides, Liu and Ciceronne, 1977; Sze, 1977; and Hameed, Pinto and Stewart 1979) of future increases of CH4 and CO. A photochemical model is used to look backwards in time by simulating the trace-gas composition of the unpolluted troposphere at the start of the industrial era (taken as 1860) and at intervals up to 1985. It is found that the OH concentration in the background troposphere has decreased significantly and O3 has increased due to increases of CH4 and CO; calculated changes depend on temporal trends of NOx (NOx = NO + NO2), for which no historical data are available. The calculations allow recent trace-gas trends affecting background chemistry and climate to be viewed in a longer-term context.

Thompson, A. M.↗

Reliability and engineering sciences area. Materials research: Single junction thin film

A test bench was designed and fabricated for the purpose of improving control of hot-spot test accuracy. Electrochemical corrosion research focused on corrosion mechanisms to which both crystalline and a-Si modules may be subjected in central station applications. A variety of cells and several designs were subjected to accelerated stress tests. Humiditiy degradation rates were determined and key electrochemical failure mechanisms were identified. Software was developed for the prediction of power loss resulting from open circuits in an array field of a-Si modules. Failure analysis was continued on the four ARCO Solar Genesis modules. The interactions of water on the silicon module was examined. An autocatalytic photooxidation model was proposed. The reliability and durability of bonding materials and electrical insulation were also studied.

Source record↗

Efficient near ultraviolet light induced formation of hydrogen by ferrous hydroxide

A possible origin of early hydrogen by UV-induced photoreduction of ferrous ions was investigated by measuring the rate of H2 formation from irradiated FeSO4 solutions as a function of pH and the range of UV sources. It was found that, in addition to the known reaction in acid solution which decreases in yield with increasing pH and requires far-UV light, there is an efficient reaction occurring between pH 6 and 9 which utilizes near-UV light (of a 200-W mercury arc lamp). This latter reaction is a linear function of both the concentration of Fe(2+) and the light intensity. These results support the suggestion of Braterman et al. (1983) that the near-UV-driven photooxidation of ferrous ions may be responsible for the origin of the banded iron formations on the early earth. The efficient photoreaction could also explain the source of reducing equivalents for CO2 reduction.

Borowska, Zofia K.↗

Discrete fluorescent saturation regimes in multilevel systems

Using models of multilevel atoms, the fluorescent process was examined for the ratio of the photooxidation rate, Pij, to the collisional oxidation rate, Cij, in the pumped resonance transition i-j. It is shown that, in the full range of the parameter Pij/Cij, there exist three distinct regimes (I, II, and III) which may be usefully exploited. These regimes are defined, respectively, by the following conditions: Pij/Cij smaller than about 1; Pij/Cij much greater than 1 and Pij much lower than Cki; and Pij/Cij much greater than 1 and Pij much higher than Cki, where Cki is the collisional rate populating the source level i. The only regime which is characterized by the sensitivity of fluorescent-fluorescent line intensity ratios to Pij is regime I. If regime III is reached, even fluorescent-nonfluorescent line ratios become independent of Pij. The analysis is applied to the resonant photoexcitation of a carbonlike ion.

Kastner, S. O.↗

Photochemistry of biogenic emissions over the Amazon forest

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

Jacob, Daniel J.↗

Electron Spin Resonance (ESR) detection of active oxygen species and organic phases in Martian soils

The presence of active oxygen species (O(-), O2(-), O3(-)) and other strong oxidants (Fe2O3 and Fe3O4) was invoked in interpretations of the Viking biological experiments and a model was also suggested for Martian surface chemistry. The non-biological interpretations of the biological results gain futher support as no organic compounds were detected in the Viking pyrolysis-gas chromatography mass spectrometer (GCSM) experiments at concentrations as low as 10 ppb. Electron spin resonance (ESR) measures the absorption of microwaves by a paramagnetic and/or ferromagnetic center in the presence of an external field. In many instances, ESR has the advantage of detailed submicroscopic identification of the transient species and/or unstable reaction intermediates in their environments. Since the higly active oxygen species (O(-), O2(-), O3(-), and R-O-O(-)) are all paramagnetic in nature, they can be readily detected in native form by the ESR method. Active oxygen species likely to occur in the Martian surface samples were detected by ESR in UV-irradiated samples containing MgO. A miniaturized ESR spectrometer system can be developed for the Mars Rover Sample Return Mission. The instrument can perform the following in situ Martian samples analyses: detection of active oxygen species; characterization of Martian surface chemistry and photooxidation processes; and searching for organic compounds in the form of free radicals preserved in subsoils, and detection of microfossils with Martian carbonate sediments.

Tsay, Fun-Dow↗

The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably required to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. It is shown that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. It has been shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

Mauzerall, David C.↗

Infrared measurements of HF and HCl total column abundances above Kitt Peak, 1977-1990 - Seasonal cycles, long-term increases, and comparisons with model calculations

The paper deals with hydrogen-chloride and hydrogen-fluoride total column measurements, their estimated long-term rates of increase, seasonal cycles, and variability, deduced from the analysis of a set of high-resolution infrared solar spectra recorded at Kitt Peak. The Kitt Peak observations and methods of analysis are described, the results are presented and compared with previously reported measurements and trends. The data is analyzed by using a multilayer nonlinear least-squares spectral fitting procedure and a consistent set of spectroscopic line parameters. Model-calculated hydrogen-chloride and hydrogen-fluoride total columns obtained with a two-dimensional model are discussed, and the model results are compared with the measured hydrogen-chloride and hydrogen-fluoride total columns, seasonal cycles, and trends. It is pointed out that the observed trends of both molecules are in satisfactory agreement with the model results calculated from emission histories and photooxidation rates for the source molecules.

Rinsland, C. P.↗

An upper limit for the rate coefficient of the reaction of NH2 radicals with O2 using FTIR product analysis

Fourier transform infrared spectrometry has been used to study the products of the photooxidation of ammonia in the presence of oxygen at 296 K. The data have been used to derive an upper limit of 6 x 10 exp -21/cu cm molecule s for the reaction of NH2 radicals with O2 to produce NO(x) at 296 K. This upper limit, which is three orders of magnitude lower than previous estimates based on the kinetics of NH2 loss, rules out the importance of this reaction in the atmosphere and suggests that NH2 will be oxidized by O3 or NO2. The effect on the NO(x) and N2O budgets depends critically on the products of the NH2 + O3 reaction. Simulations of the experimental product yields also allow an evaluation of possible product channels for the reaction of NH2 with HO2.

Tyndall, G. S.↗

The photochemistry of manganese and the origin of banded iron formations

The origin of the deposition of superior-type Precambrian banded iron formations (BIFs) is investigated in experiments where the effect of UV radiation on dissolved manganese was studied to determine if the commonly accepted photochemical model for BIF formation is consistent with the distribution of Mn in BIFs. Solutions containing 0.56 M NaCl and about 180 microM MnCl2, with or without 3 to 200 microM FeCl2 were irradiated with filtered and unfiltered UV light for up to 8 hrs; the solutions were deaerated and buffered to a pH of 7, and the experiments were conducted under oxygen-free atmosphere. Data on the rate of manganese photooxidation confirmed that a photochemical model for the origin of oxide facies BIFs is consistent with field observations.

Anbar, A. D.↗

Reactive nitrogen oxides and ozone above a taiga woodland

Measurements of reactive nitrogen oxides (NO(x) and NO(y)) and ozone (O3) were made in the planetary boundary layer (PBL) above a taiga woodland in northern Quebec, Canada, during June-August, 1990, as part of NASA Artic Boundary Layer Expedition (ABLE) 3B. Levels of nitrogen oxides and O3 were strongly modulated by the synoptic scale meteorology that brought air from various source regions to the site. Industrial pollution from the Great Lakes region of the U.S. and Canada appears to be a major source for periodic elevation of NO(x), and NO(y) and O3. We find that NO/NO2 ratios at this site at midday were approximately 50% those expected from a simple photochemical steady state between NO(x) and O3, in contrast to our earlier results from the ABLE 3A tundra site. The difference between the taiga and tundra sites is likely due to much larger emissions of biogenic hydrocarbons (particularly isoprene) from the taiga vegetation. Hydrocarbon photooxidation leads to relatively rapid production of peroxy radicals, which convert NO to NO2, at the taiga site. Ratios of NO(x) to NO(y) were typically 2-3 times higher in the PBL during ABLE 3B than during ABLE 3A. This is probably the result of high PAN levels and suppressed formation of HNO3 from NO2 due to high levels of biogenic hydrocarbons at the ABLE 3B site.

Bakwin, Peter S.↗

Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

Non-NASA Center↗