Investigation of degradation mechanisms in PEM fuel cells caused by low-temperature cycles

Environmental influences, especially temperatures below the freezing point, can affect the performance and long-term stability of PEMFCs. Within the scope of this research, a completely new test procedure was developed to characterize PEMFC single cells with respect to their long-term stability at temperature cycles between 80 °C and ?10 °C. Using this procedure, the behavior of PEMFC single cells (active surface area of 43.6 cm²) with different cathode-ionomer-to-carbon (I/C) weight ratios (0.5/1.0/1.5) was evaluated. The generated in-situ measurement data clearly demonstrate that the performance of each PEMFC single cell changes individually as a function of the cathode I/C-ratio during the 120 stress cycles. While the MEA with an I/C ratio of 0.5 showed a power loss of ~1.49%, the MEAs with an I/C ratio of 1.0 and 1.5 showed a power loss of about ~7.75% and ~24.7%, respectively. The subsequent post-mortem ex-situ analyses clearly showed how the test procedure and the different I/C-ratios affected the changes in the catalyst layers (CL). The destructive mechanisms responsible for the changes can be divided into two categories: One part was driven by rapid enthalpy change leading to mechanical failure, and the other part, which led to the reduction of cathode CL thickness, was driven by rapid potential changes and potential shifts (overpotentials). This reduction in cathode CL thickness ultimately leads to an accumulation and excessive load of ionomer in the direction of GDL, resulting in a reduction in pore size, a shift in the core reaction area, and high O₂ transport resistance.     

La4Ni3O10±δ – BaCe0.9Y0.1O3-δ cathodes for proton ceramic fuel cells; short-circuiting analysis using BaCe0.9Y0.1O3-δ symmetric cells

Protonic ceramic fuel cells are a promising technology for energy conversion and chemical synthesis in the intermediate temperature range (400–600 °C). Nevertheless, a major restriction to their wider implementation concerns their relatively high cathode polarisation resistance that can become performance limiting as working temperatures decrease. As potential new cathode materials, high order nickelates can be attractive candidates as they exhibit high electrical conductivities at lower temperatures due to their metallic behaviour. In the current work, we investigate the performance of La₄Ni₃O_10±δ and La₄Ni₃O_10±δ–BaCe_0.9Y_0.1O_3-δ composite cathodes, deposited on a BaCe_0.9Y_0.1O_3-δ (BCY10), proton-conducting electrolyte in the temperature range 350–550 °C. The study is performed in symmetrical cell configuration to permit separation of the electrode performance from the overall cell behaviour. For such experiments, possible internal short-circuiting of the electrolyte in oxidising conditions can arise from the presence of p-type electronic conductivity in the BCY10 electrolyte, causing underestimation of measured polarisation resistances. The current work corrects for such factors by knowledge of the transference numbers of the BCY10 electrolyte and the use of a parallel short-circuiting resistor in the equivalent circuit model. The results underscore that the cathode characteristics are highly dependent on the electronic leakage, especially at higher temperatures, and that suitable correction of data is imperative before discussion. Corrected values for polarisation resistance in wet O₂ reveal the composite cathode shows an improvement of total polarisation resistance by a factor of 1.5. The analysis on the oxygen reduction reaction mechanism allows the rate-limiting processes between the electrodes to be differentiated, with the low-frequency term, corresponding to surface processes, being the dominant polarisation resistance and the most improved on formation of the composite. Overall performance analysis indicates that the results from this work are in line with some of the best cathodes currently reported.     

Femtosecond resonance enhanced CARS for background-free detection of organic molecules

We study the coherent excitation profile (CEP) of resonance enhanced femtosecond CARS in a model system zinc phthalocyanine in a polymer film host as a prospective technique for detection and identification of molecular species in ambient environments. A new method of suppressing the non-resonant FWM background is demonstrated. Transform theory is applied to calculate CEP based on the absorption spectrum, and good agreement between theory and experiment is obtained.     

Analysis of the Thermal Performance of SODI Instrument for DCMIX Configuration

There exists an instrument SODI (Selected Optical Diagnostic Instrument) on the ISS where series of the DCMIX (Diffusion Coefficients in Mixtures) experiments are conducted by members of the ESA Topical Team. The study is addressed to the performance of thermal design of SODI instrument for DCMIX configuration. We report the results on the temperature fields which were measured interferometrically both in two ground setups (one thermally optimized; the other one, the engineering model of the ISS SODI-DCMIX experiment: non optimized) and in the ISS experiment itself with the respective numerical simulations. Even though monitoring of the cell with binary mixture $THN-nC_{12}$ employs only an interferometer with one wave length instead of two for other cells with ternary mixtures, it gives valuable information about the instrument performance. Temperature and concentration fields observed during the tests in the engineering model are compared with those obtained in laboratory experiments with the same liquid, with numerical simulations and with first results from the ISS in Run #16. The thermal design of the microgravity cell, being not optimized for ground experiments, exhibits a promising performance in the weightlessness condition.     

Enhancing grid security by fine-grained behavioral control and negotiation-based authorization

Nowadays, Grid has become a leading technology in distributed computing. Grid poses a seamless sharing of heterogeneous computational resources belonging to different domains and conducts efficient collaborations between Grid users. The core Grid functionality defines computational services which allocate computational resources and execute applications submitted by Grid users. The vast models of collaborations and openness of Grid system require a secure, scalable, flexible and expressive authorization model to protect these computational services and Grid resources. Most of the existing authorization models for Grid have granularity to manage access to service invocations while behavioral monitoring of applications executed by these services remains a responsibility of a resource provider. The resource provider executes an application under a local account, and acknowledges all permissions granted to this account to the application. Such approach poses serious security threats to breach system functionality since applications submitted by users could be malicious. We propose a flexible and expressive policy-driven credential-based authorization system to protect Grid computational services against a malicious behavior of applications submitted for the execution. We split an authorization process into two levels: a coarse-grained level that manages access to a computational service; and a fine-grained level that monitors the behavior of applications executed by the computational service. Our framework guarantees that users authorized on a coarse-grained level behave as expected on the fine-grained level. Credentials obtained on the coarse-grained level reflect on fine-grained access decisions. The framework defines trust negotiations on coarse-grained level to overcome scalability problem, and preserves privacy of credentials and security policies of, both, Grid users and providers. Our authorization system was implemented to control access to the Globus Computational GRAM service. A comprehensive performance evaluation shows the practical scope of the proposed system.

Parameters of high temperature steam gasification of original and pulverised wood pellets

Experiments on gasification of chars obtained from original and pulverised wood pellets were conducted in atmosphere of water steam and nitrogen under temperatures of 800, 900 and 950 °C. Molar flow rates of carbon containing product gases were measured and approximated using different models with respect to extents of carbon conversion in char of the pellets. Comparison of the random pore, grain and volumetric models revealed the best applicability for approximations of the random pore model. Apparent activation energies obtained as a result of application of the models to the data from experiments with char of original pellets were higher in comparison to those of pulverised pellets, except for a grain model. Approximations under 800 °C showed relatively big deviations from experimental data on the beginning of char gasification. This is attributed to catalytic effects from alkali metals in the pellets.     

Optical properties of composite heterophase objects with liquid crystal material for different display applications

Liquid crystal (LC) director distribution and optical transmission for different types of heterophase systems with different LC boundary conditions is simulated. The first type is a transparent isotropic material with spherical or cylindrical liquid crystalline objects. There are polymer dispersed liquid crystal, LC fiber, lyotropic LC in polarizing films, LC in microgroove and nanogrooves and pores. The second type is an LC layer incorporating an isotropic transparent or non‐transparent object like microparticles and nanoparticles, spacers, protrusions in multi‐domain vertical alignment LC display et al. The system parameters' influence on LC display performances is discussed.     

Stateful Data Usage Control for Android Mobile Devices

Modern mobile devices allow their users to download data from the network, such as documents or photos, to store local copies and to use them. Many real scenarios would benefit from this capability of mobile devices to easily and quickly share data among a set of users but, in case of critical data, the usage of these copies must be regulated by proper security policies. To this aim, we propose a framework for regulating the usage of data when they have been downloaded on mobile devices, i.e., they have been copied outside the producer’s domain. Our framework regulates the usage of the local copy by enforcing the Usage Control policy which has been embedded in the data by the producer. Such policy is written in UXACML, an extension of the XACML language for expressing Usage Control model-based policies, whose main feature is to include predicates which must be satisfied for the whole execution of the access to the data. Hence, the proposed framework goes beyond the traditional access control capabilities, being able to interrupt an ongoing access to the data as soon as the policy is no longer satisfied. This paper details the proposed approach, defines the architecture and the workflow of the main functionalities of the proposed framework, describes the implementation of a working prototype for Android devices, presents the related performance figures, and discusses the security of the prototype.     

Pyrolysis study of halogen-containing aromatics reflecting reactions with polypropylene in a posttreatment decontamination process

Halogen-containing aromatics, mainly bromine-containing phenols, are harmful compounds contaminating pyrolysis oil from electronic boards containing halogenated flame retardants. In addition,theirformation increases the potential for evolution of polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs) at relatively low temperature (up to 500 degrees C). As a model compound, 2,4-dibromophenol (DBP) was pyrolyzed at 290-450 degrees C. While its pyrolysis in a nitrogen flow reactor or in encapsulated ampules yields bromine-containing phenols, phenoxyphenols, PBDDs, and PBDFs, pyrolysis of DBP in a hydrogen-donating medium of polypropylene (PP) at 290-350 degrees C mainly results in the formation of phenol and HBr, indicating the occurrence of a facile hydrodebromination of DBP. The hydrodebromination efficiency depends on temperature, pressure, and the ratio of the initial components. This thermal behavior of DBP is compared to that of 2,4-dichlorophenol and decabromodiphenyl ether. A treatment of halogen-containing aromatics with PP offers a new perspective on the development of low-environmental-impact disposal processes for electronic scrap.     

Scattering matrix approach to the resonant states and Q values of microdisk lasing cavities

We develop a scattering matrix approach for the numerical calculation of resonant states and Q values of a nonideal optical disk cavity with an arbitrary shape and with an arbitrary varying refraction index. The developed method is applied to study the effect of surface roughness and inhomogeneity of the refraction index on Q values of microdisk cavities for lasing applications. We demonstrate that even small surface roughness (deltar < or approximately equal to lambda/50) can lead to a drastic degradation of high-Q cavity modes by many orders of magnitude. The results of the numerical simulation are analyzed and explained in terms of wave reflection at a curved dielectric interface, combined with an examination of Poincaré surfaces of section and of Husimi distributions.