Degradation of semiconducting polymers by concentrated sunlight

A lens based sunlight concentration setup was used to accelerate the degradation of semiconducting polymers. Sunlight was collected outdoor and focused into an optical fiber bundle allowing for indoor experimental work. Photo-degradation of several polymers was studied by UV-vis absorbance spectroscopy and infra-red spectroscopy. This showed that the degradation rate is significantly increased by increasing illumination intensity. Acceleration factors exceeding 100 compared to standard 1 sun illumination were observed for solar concentration of 200 suns in the case of P3HT. A comparison between infra-red spectra of MEH-PPV degraded at 1 sun intensity and at high solar concentration only showed minor deviations in degradation mechanisms. The acceleration factor was found to vary linearly with the solar concentration. Finally, a comparison of the degradation rates at 1 sun and 100 suns was carried out in a materials study employing five different conjugated polymers relevant to polymer solar cells for which acceleration factors in the range 19-55 were obtained.     

Aging of electrochemical double layer capacitors with acetonitrile-based electrolyte at elevated voltages

Laboratory-scale electrochemical capacitor cells with bound activated carbon electrodes and acetonitrile-based electrolyte were aged at various elevated constant cell voltages between 2.75 V and 4.0 V. During the constant voltage tests, the cell capacitance as well as the capacitance and resistance of each electrode was determined. Following each aging experiment, the cells were analyzed by means of electrochemical impedance spectroscopy, and the individual electrodes were characterized by gas adsorption and X-ray photoelectron spectroscopy. At cell voltages above 3.0 V, the positive electrode ages much faster than the negative. Both the capacitance loss and resistance increase of the cell could be totally attributed to the positive electrode. At cell voltages above 3.5 V also the negative electrode aged significantly. X-ray photoelectron spectroscopy indicated the presence of degradation products on the electrode surface with a much thicker layer on the positive electrode. Simultaneously, a significant decrease in electrode porosity could be detected by gas adsorption.     

Tribochemical Surface Reaction and Lubricating Oil Film

A radioactive tracer technique was used to investigate a tribo-chemical surface reaction obtained by a thrust collar type friction Machine. Radioactive dibenzyl disulfide labeled with sulfur-35 was used as an additive. Steel and copper disks were used as friction specimens.

Radioactive copper sulfide on the friction surface was quantitatively measured with a G-M tube, and a kinetical analysis of the reaction was carried out.

The friction coefficient decreased linearly depending on the amount of surface produced on the friction surface. This dependency was accompanied by adsorption of dibenzyl disulfide, which made a more effective lubricating oil film and was enhanced by the sulfide on the friction surface.

The results of kinetical analysis were explained effectively by considering the oil film behavior related to the adsorptive action of the surface sulfide.     

Micro modelling of solid oxide electrolysis cell: From performance to durability

An in-house micro model has been built to describe the electrochemical mechanisms governing both H₂ and O₂ electrodes operating in SOEC mode. A special attention has been paid to take into account the microstructure properties of the ionic, electronic and gas phases as well as the processes occurring therein.     

Extreme Pressure Lubrication and Wear. The Chemical Reactivity and the Extreme Pressure Action of Two Aliphatic Disulfides

Reaction rates were studied for the action of di-tert-octyl disulfide and di-n-cetyl disulfide in white oil on iron powder over the temperature range 165–250 C. The data were fitted to the Arrhenius equation, and the tertiary disulfide was found to be 1500 times as reactive as the normal disulfide. White oil solutions of the two disulfides were subjected to the Falex test and to the four-ball extreme-pressure test, and the tertiary disulfide was found to be the more effective lubricant additive in these tests. Wear studies were carried out with a pin and disk apparatus under conditions which approximated the above bench tests as regards specimen material, rubbing speed and pressure. The complex nature of the course of wear made it difficult to compare the two disulfides quantitatively. It was found that the tertiary disulfide was 2 to 20 times as efficacious as the normal disulfide in reducing the terminal steady-state wear rate. By treating the additive action of the disulfides as a competition between the rate of metallic adhesion and the rate of chemical reaction with iron, it is possible to reconcile the wide discrepancy between the relative chemical reactivity and the relative additive action of the two disulfides in a quantitative fashion.     

Fuel cell micro-CHP techno-economics: Part 2 – Model application to consider the economic and environmental impact of stack degradation

This article presents a literature review regarding the mechanisms of fuel cell degradation, accompanied by the reported range of observed degradation rates in experimental, demonstration and early commercial systems. It then synthesises and exploits this information to investigate the influence of degradation on the economic and environmental credentials of fuel cell micro-combined heat and power (micro-CHP) for the UK residential sector. The investigation applies a techno-economic model developed in the companion article designed to demarcate the key characteristics of commercially successful systems. Two distinct modes of degradation are examined; one proportional to power density in the stack, and the other proportional to thermal-cycling rate of the stack. It is found that limiting the power-density related degradation rate is very important from economic and environmental viewpoints, but thermal-cycling related degradation is less important when thermal energy storage is available because cycling can be avoided. Furthermore it is noted that techno-economic studies that ignore degradation can overestimate the marginal value of a micro-CHP system with respect to the conventional alternative by up to 45% and the CO₂ emissions reduction potential by up to 57%, for performance degradation rates of 2% per MW_eh output. This conclusion is noteworthy because most techno-economic analyses of fuel cells ignore degradation, potentially providing misleading results. Finally it is concluded that existing commercial degradation targets, such as the SECA targets, are appropriate for achieving marketable systems.     

Identification and analysis of Swiss National Road tunnels pathologies

In order to evaluate the general conditions (i.e. safety, serviceability and durability) of tunnels, a detailed analysis of the lining structure and surrounding rock mass is required. During the service life of the tunnel, regular survey activities should be performed to check the tunnel conditions and regular conservation practices are necessary to preserve the tunnel’s structural integrity and guarantee safety and serviceability during operation. The collection of data about tunnels since their construction and during their service life may help in the assessment of tunnel conditions and improve the understanding of tunnel degradation with time. The long term behaviour of the Swiss National Road tunnels has been studied and a specific data base has been developed. Based on detailed literature review and analysis of principal inspections results collected in the data base, the main pathologies that affect the Swiss road tunnels have been identified. In addition, by means of a specific data analysis, both degradation potential and rate have been investigated and the main influence factors involved have been selected. The obtained results confirm what was expected according to observations in the past. After a brief introduction about the tunnels of the National Roads network, this paper describes the main steps of the data analysis, different methods used and main results of the analysis. Due to the fact that the tunnels within Swiss National Roads were developed during the 60s, attention has been focused only on concrete lined tunnels.     

Degradation of reactive dyes in wastewater from the textile industry by ozone: Analysis of the products by accurate masses

The present work describes the use of ozone to degrade selected reactive dyes from the textile industry and the analysis of the resulting complex mixture by liquid chromatography/mass spectrometry (LC-MS). To allow certain identification of the substances detected in the wastewater, the original dyes were also investigated either separately or in a synthetic mixture of three dyes (trichromie). Since the reactive dyes are hydrolyzed during the dyeing process, procedures for the hydrolysis were worked out first for the individual dyes. The ozonated solutions were concentrated by solid-phase extraction, which separated very polar or ionic substances from moderately polar degradation products. The latter, which are the primary degradation products, were investigated by liquid chromatography/mass spectrometry with a tandem quadrupole time-of-flight mass analyzer. Accurate masses, which in most cases could be determined with a deviation of ≤5 ppm from the exact value, were also measured. In addition, a diode-array detector was placed before the mass analyzer to provide UV-vis spectra of the products in the same run. With retention times, mass spectra, accurate masses, UV-vis spectra and, of course, knowledge of the structures of the original dyes, plausible structures could be proposed for most of the components of the moderately polar fraction. These structures were confirmed by ¹H NMR in cases where it was practical to isolate the degradation products by preparative HPLC.     

The significance of fullerene electron acceptors in organic solar cell photo-oxidation

Stability of organic solar cells requires development before their commercialisation is possible. This review will give a brief overview of organic solar cells and their stability, before focussing on the photochemical stability of the active layer. The photo-oxidation of the donor polymers will be looked at first which has been studied quite extensively and then fullerene electron acceptors, such as widely used phenyl-C61-butyric acid methyl ester, which has been considerably less studied. It has been shown that oxidation of the fullerene cage on phenyl-C61-butyric acid methyl ester results in oxides with a deeper lowest unoccupied molecular orbital (LUMO) level than the fresh electron acceptor. These oxides act as electron traps, leading to deterioration of the blend photoconductivity. The significance of fullerene photo-oxidation on device stability has been indirectly shown via research on: photoconductivity; organic solar cells made with an oxidised fullerene derivative and organic field effect transistors. Techniques that could be developed to increase photochemical stability of fullerene electron acceptor resistance to photo-oxidation include: reducing its LUMO level; increasing its crystallinity or aggregation and changing its chemical structure. Improving the photochemical stability of organic solar cells would move us one step closer to a more accessible solar power.     

On using available environmental data in service life estimations

In the process of service life prediction or estimation of building and construction components and materials, data of the prevailing exposure environment, (the conditions at and around a building or construction) is required. However, most environmental data is measured by and available from meteorological and air quality research communities. This data is collected at macro and meso levels, some distance from the object studied, and raises the need to transform data in order to describe the specific, local conditions adjacent to that object. To estimate levels of degradation agents in the exposure environment, especially those close to the building or construction at local and micro levels have to be considered. This paper will show and discuss useful environmental data sources, and how to transform such data by means of available distribution models.

Lorsqu'il s'agit de faire des prévisions ou des estimations de durée de vie de bâtiments ainsi que de composants et matériaux de construction, il faut disposer des données sur les conditions prévalantes d'exposition et d'environnement (conditions qui règnent dans un bâtiment ou à proximité). Or, la plupart des données environnementales sont mesurées et fournies par des instituts de recherche en météorologie et qualité de l'air. Ces données sont collectées à grande et à moyenne échelle, à une certaine distance de l'objet étudié, et elles doivent donc être transformées si l'on veut décrire les conditions spécifiques locales à proximité dudit objet. Pour estimer le niveau de dégradation dans l'environnement d'exposition, notamment à proximité des bâtiments ou constructions, il faut considérer les agents au micro-niveau et au niveau local. Cet article présente et examine des sources de données environnementales utiles et montre comment transformer ces données en utilisant les modèles de distribution existants.