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.     

Coke Formation from Aircraft Engine Oils: Part II—Effects of Oil Formulation and Surface Composition

This is the second of two papers giving the results of a study undertaken to determine how aircraft engine oil degrades to form coke on oil-wetted surfaces. In part 2 the authors address the impacts of additives (which is related to oil types) and surface materials upon the oil coking process.

In Part 1 of this study, the authors showed that simple laboratory tests involving thin films of oil heated for specified timesltemperatures in open glass vials produced polymer and coke similar to the deposits seen on failed face seals taken from the operating aircraft engines and polymers isolated from used engine oils. Antioxidants inhibit and delay the coke producing reactions. After the antioxidant package is depleted to approximately 10 percent of the original level, the ester basestock undergoes accelerated oxidation to form oil-soluble polymers. As the oil spends additional time at elevated temperature, these polymers increase in molecular weight and undergo minor compositional changes becoming insoluble in the oil, producing deposits. If the time that a thin oil layer spends on a hot surface at elevated temperature can be limited so that the antioxidant does not deplete completely, coking can be prevented. This shifts the focus from coke minimization to coke prevention.

The authors results in Part 2 indicate that oil choice—which is largely a choice of antioxidant package—makes a large difference in how long oil can remain on a hot surface without forming polymer/coke deposits. For the oils studied in Part 2, the capabilities of the oils' antioxidant packages to inhibit coke formation varied 15 fold.

Surface material choice has minimal effect upon the rate of antioxidant depletion. However, once the antioxidant in the oil in a thin layer has become ineffective in inhibiting accelerated oxidation (approximately 10 percent of original concentration), the material the oil resides upon strongly effects the rate of the polymer/coke formation processes. Stainless steel speeds the process compared to a glass substrate.     

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.     

Impact of synchrotron radiation on fuel cell operation in imaging experiments

For the clarification of water transport mechanisms in operating fuel cells, synchrotron radiation computed tomography (SR-CT) was applied. A novel fuel cell has been designed that exposes the entire active area (7 mm²) to the SR beam while at the same time allowing for full fuel cell operation during the imaging experiment. This micro fuel cell has been qualified successfully prior to the SR imaging experiments. The cell voltage was 600 mV at 0.2 A cm⁻² (open circuit voltage, OCV > 950 mV) and the operation was stable for hours. However, under SR beam exposition for in situ imaging, severe cell performance degradation within minutes has been reproducibly observed. Even after the SR beam had been switched-off cell operation remained irreversibly degraded whilst OCV could be recovered. Preliminary results indicate a higher degradation sensitivity of the cathode side of the cell. Apparently, the unique setup of the experiment which exposes an operating fuel cell with the entire active area to the SR beam reveals otherwise unnoticeable degradation mechanisms. It may have to be concluded that the very same materials degrade heavily during beam exposure that are subject of the imaging investigation. Consequently, the applicability of SR imaging to study water transport in porous fuel cell materials has to be revisited critically. This publication describes the observations made during fuel cell operation under SR beam exposure and discuss potential mechanisms that may cause beam-induced performance degradation.     

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.     

In situ spectroelectrochemical measurements during the electro-oxidation of ethanol on WC-supported Pt-black. Part II: Monitoring of catalyst aging by in situ Fourier transform infrared spectroscopy

As a continuation of a project on the spectroelectrochemical analysis of long-term behaviour of WC-supported Pt electrocatalysts (for SFG results, see part I: [1]), in this paper we report in situ FT-IR spectroscopy experiments, carried out during prolonged electro-oxidation of ethanol on Pt-black. From the analytical point of view, as expected, FT-IR spectra showed the presence of adsorbed acetic acid and ethanol, in addition to the well-known, dominant species: linearly adsorbed CO (2044-2063 cm⁻¹) and solution-phase CO₂ (2345 cm⁻¹). As far as quantitative spectroscopic results are concerned, a notable sensitivity of the interfacial chemistry to catalyst aging could be highlighted by this approach. The spectra recorded in three subsequent series of potential-cycling experiments showed a clear-cut dependence of spectral patterns and peak intensities, on the applied potential and on the oxidation duration. Qualitative spectral changes seem to suggest - coherently with in situ SFG results obtained with the same system [1] - that electrocatalyst aging correlates with a higher surface coverage with ethanol as compared with acetic acid. Quantitative analysis, based on fitting with Lorentzian lineshapes, yields information that can be used as a molecular-level diagnostic of the modification of the catalyst-adsorbate structure.     

Stability Indicating HPTLC Determination of Linezolid as Bulk Drug and in Pharmaceutical Dosage Form

Abstract

A simple, selective, precise, and stability-indicating high-performance thin layer chromatographic method of analysis of Linezolid both as a bulk drug and in formulations was developed and validated in pharmaceutical dosage form. The method employed TLC aluminium plates precoated with silica gel 60F-254 as the stationary phase. The solvent system consisted of toluene–acetone (5:5, v/v). This system was found to give compact spots for Linezolid (R_f value of 0.29 ± 0.01). Linezolid was subjected to acidic, alkali hydrolysis, oxidation, and photodegradation. The degraded products also were well separated from the pure drug. Densitometric analysis of Linezolid was conducted in the absorbance mode at 254 nm. The linear regression data for the calibration plots showed good linear relationship with r² = 0.997 ± 0.001 in the concentration range of 300–800 ng/spot. The mean value of correlation coefficient, slope, and intercept were 0.998 ± 0.003, 0.15 ± 0.009, and 19.52 ± 1.66 respectively. The method was validated for precision, accuracy, ruggedness, and recovery. The limits of detection and quantification were 20 ng/spot and 50 ng/spot, respectively. The drug undergoes degradation under acidic and basic conditions, oxidation and photo degradation. All the peaks of degraded product were resolved from the standard drug with significantly different R_f values. This indicates that the drug is susceptible to acid–base hydrolysis, oxidation, and photo degradation. Statistical analysis proves that the method is reproducible and selective for the estimation of the said drug. Because the method could effectively separate the drug from its degradation products, it can be used as a stability indicating one.     

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.     

Particle-induced Phagocytic Cell Responses are Material Dependent: Foreign Body Giant Cells Vs. Osteoclasts from a Chick Chorioallantoic Membrane Particle-implantation Model

There is increasing concern about particles generated from wear-prone implants that are placed in body tissues, including artificial hip, knee, and jaw joints. Although phagocytes and foreign body giant cells are associated with inhaled or embedded particulate debris, some particles also induce bone digestion by eliciting the differentiation and proliferation of highly specialized osteoclastic cells. This report describes the differential phagocytic cellular responses to four implant-related types of ground, model wear particles in a live-egg cell-response model, as implants to the chick chorioallantoic membrane (CAM): polymethylmethacrylate (PMMA), a main constituent of some temporomandibular joint (TMJ) implants and orthopedic cements used to retain artificial hips and knees; Proplast-HA, an implantable composite of polytetrafluoroethylene (PTFE) and degradable mineral (hydroxyapatite) that has been associated with bone erosion around failed TMJ implants; talc, a nondegradable mineral sometimes found in tissues as a contaminant from talc-coated surgical gloves; and authentic bone, known to induce the formation of osteoclastic cells. Light and electron microscopy of CAM tissues harvested, sectioned and stained with special reagents for the enzymes tartrate-resistant acid phosphatase (TRAP) and tartrate-resistant adenosine triphosphatase (TrATPase), and for the osteoclast-specific antigen 121F, showed that only authentic bone and the degradable HA-rich particles induced osteoclast formation. From these results, and supporting data with polypropylene particles, it is concluded that nonbiodegradable polymer particles, alone, do not induce bone dissolution. Inert polymers do induce foreign body giant cells without the external mineral digestion qualities unique to osteoclasts, however. The chick embryo model system allows quick and affordable examination of material-dependent differences in phagocytic cellular responses to implant wear debris and particles from various occupational environments.