Dense silicon carbonitride ceramics by pyrolysis of cross-linked and warm pressed polysilazane powders

This study reports on the pyrolysis and densifaction behavior of cross-linked poly(hydridomethylsilazane) powders. The influence of the cross-linking procedure such as temperature and annealing time of the polymer powders on the compaction behavior under cold and warm pressing conditions is discussed. The degree of cross-linking is determined by thermal mechanical analysis (TMA). In addition to particle sliding which is assumed to be the compaction mechanism obtained by cold-pressing, the polymer powder consolidates by plastic deformation applying warm-pressing. A continuous 3-dimensional polysilazane network is formed after a dwelling time under these conditions. Pyrolysis of the cross-linked and compacted polysilazane powder in argon at 1100°C gives crack-free amorphous silicon carbonitride Si_3+xC_x+yN₄ with compositions ranging from x=1·47 and y=0·88 for cold pressed samples to x=1·47 and y=1·86 for warm pressed materials. The residual open porosity is significantly reduced from 10–15 vol% in the cold pressed specimens to 1·3–5 vol% by the warm pressing procedure. The weight loss during pyrolysis between room temperature and 1300°C is about 5 wt% lower than that for cold pressed specimens. This result is explained by a reduced methane evolution during the polymer-to-ceramic conversion and is in accordance with the enhanced carbon content of the warm pressed material.     

Compound-specific factors influencing sorption nonlinearity in natural organic matter

Nonlinear sorption by natural organic matter may have a significant impact on the behavior of organic contaminants in soils and sediments. This study presents a molecular probe approach based on linear solvation energy relationships (LSERs) to identify and quantify the molecular interactions causing concentration-dependent sorption and proposes estimation methods for sorption nonlinearities. Sorption isotherms ranging over concentrations of more than 4 orders of magnitude were determined in batch systems for 23 and 16 chemically diverse probe compounds in a lignite sample and a peat soil, respectively. Each sorbent showed characteristic nonlinear sorption with Freundlich exponents (1/n) being 0.7-1. The LSER-based analysis revealed that the strength of nonspecific interactions did not vary with concentration for both sorbents. In lignite, specific interactions did not affect sorption nonlinearity either, suggesting that compound-independent factors of lignite were responsible for the nonlinear sorption. In the peat soil, by contrast, the specific interactions related to the solute polarizability/dipolarity parameter (S) decreased with increasing concentration. Consequently, compounds of higher S values were more susceptible to nonlinear sorption in the peat soil. Phenol probes have shown that hydrogen bond donating properties of sorbate compounds have a substantial impact on the overall strength of sorption with organic matter, but no significant influence on sorption nonlinearity. Heterocyclic aromatic compounds appear to undergo additional interactions that are not accounted for by the LSER. These additional interactions considerably enhance both sorption capacity and nonlinearity.     

The potential for large-scale savings from insulating residential buildings in the EU

Energy used in buildings is responsible for more than 40% of energy consumption and greenhouse gas (GHG) emissions of the EU and their share in cost-efficient GHG mitigation potentials is estimated to be even higher. In spite of its huge savings potential of up to 80%, achievements are very slow in the building sector and much stronger political action seems to be needed. One important step in this direction has been the recast of the Energy Performance of Buildings Directive (EPBD) in autumn 2009. However, strong national implementation including powerful packages of flanking measures seems to be crucial to really make significant progress in this important field. In order to directly improve political action, we provide a differentiated country-by-country bottom up simulation of residential buildings for the whole EU, Norway, Iceland, Croatia and Liechtenstein. The analysis provides a database of the building stock by construction periods, building types, as well as typical building sizes. It includes a simulation of the thermal quality and costs of the components of the building shell for new buildings as well as the refurbishment of the existing building stock. Based on this differentiated analysis, we show in detail what would be needed to accelerate energy savings in the building sector and provide a more precise estimate of the potentials to be targeted by particular policies. We demonstrate, e.g. that the potential of building codes set via the EPBD would be located mainly in those countries that already have quite stringent codes in place. We show as well the high relevance of accelerating refurbishments and re-investment cycles of buildings. By providing a clear estimate of the full costs related to such a strategy, we highlight a major obstacle to accelerated energy-efficient building renovation and construction.     

Development and design of experiments optimization of a high temperature proton exchange membrane fuel cell auxiliary power unit with onboard fuel processor

In this work, the concept development, system layout, component simulation and the overall DOE system optimization of a HT-PEM fuel cell APU with a net electric power output of 4.5 kW and an onboard methane fuel processor are presented.A highly integrated system layout has been developed that enables fast startup within 7.5 min, a closed system water balance and high fuel processor efficiencies of up to 85% due to the recuperation of the anode offgas burner heat. The integration of the system battery into the load management enhances the transient electric performance and the maximum electric power output of the APU system.Simulation models of the carbon monoxide influence on HT-PEM cell voltage, the concentration and temperature profiles within the autothermal reformer (ATR) and the CO conversion rates within the watergas shift stages (WGSs) have been developed. They enable the optimization of the CO concentration in the anode gas of the fuel cell in order to achieve maximum system efficiencies and an optimized dimensioning of the ATR and WGS reactors.Furthermore a DOE optimization of the global system parameters cathode stoichiometry, anode stoichiometry, air/fuel ratio and steam/carbon ratio of the fuel processing system has been performed in order to achieve maximum system efficiencies for all system operating points under given boundary conditions.     

Identification of congestion and valuation of transport infrastructures in the European natural gas market

Rising import dependency, increasing market liberalization and cross-border trade and security of supply fears facilitate investments in natural gas supply infrastructures in Europe. In order to ensure an efficient allocation of capital resources, it is important to identify congestion in the existing system and investment requirements based on economic principles. This paper first outlines an analytical framework for the identification of bottlenecks and the evaluation of transport capacities and the cost of congestion based on nodal prices. Secondly, an infrastructure model of the European gas market with high temporal and spatial granularity which exhibits the characteristics of the theoretical model is introduced. Parameterizing the model with the existing infrastructure and applying a demand and supply scenario for the year 2015, congestion mark-ups between countries in Europe are estimated. This approach indicates potential bottlenecks which might arise within the next five years and quantifies their economic costs. With only some temporary congestion, physical market integration is found to be high in Western Europe. In Eastern Europe, severe bottlenecks are identified and discussed. Implications for efficient investment decisions arising from the findings are examined in the context of the theoretical considerations.     

Biomass for energy, food and materials in an industrial society of 10 billion people

In this paper we analyse the requirements of bioproductive land in a future industrial society of 10 billion people, with an average per capita economic standard comparable to that of the industrialized countries of today. Despite significantly more efficient technology, lowering demand for both energy and material per service delivered, requirement for food and material alone will call for a heavily increased demand for bioproductive land for use in agriculture and forestry. Large areas of short rotation energy plantations may be biophysically possible, but will clearly compete for available bioproductive land with agriculture and silviculture, as well as with preservation of the world's biodiversity. Therefore, the notion that there exists large areas of surplus or degraded land, which, without coming in conflict with food production and preservation of biodiversity, can be used for large energy plantations has not fully taken into account possible increased demand for bioproductive land from global industrialization and the raising of the global average economic standard.     

Thermal parameters identification of micrometric layers of microelectronic devices by thermoreflectance microscopy

The objective of this paper is the determination of the thermal properties of micrometric layers of electronic devices using a thermoreflectance probe. Unlike classical thermoreflectance methods, the main point of the method presented in this paper is to be able to quantify the heating energy (by Joule effect) and the effective temperature response (by calibration). It is then possible to estimate the thermal conductivity (in W m⁻¹ K⁻¹) instead of the thermal diffusivity (in m² s⁻¹). A semi-analytical thermal 3D-periodic model then enables to identify a few thermal properties of the layers of the device, and in particular the thermal conductivity of the passivation layer. This methodology has been applied to the study of an industrial device containing interconnect test structures made of copper lines on a silicon wafer with a few micrometers BCB (BenzoCycloButene) polymer passivation layer. The BCB thermal conductivity and the metal heat capacity are obtained using this method.     

Interaction of positronium atoms, with paramagnetic molecules, measured by perturbed angular distribution in 3γ annihilation decay

Positronium in the triplet spin state (S = 1) decays by 3γ annihilation having a life time of about 140 ns in vacuum. Positronium annihilation is affected by magnetic fields which mix the M = 0 state of ortho-positronium with the M = 0 state of para-positronium. The mixing fraction depends on the magnetic field intensity and causes quantum beats in the time distribution of γ annihilation decay. This effect was predicted by Barishevsky et al. [V.G. Barishevsky, O.N. Metelitsa, V.V. Tikhomirov, J. Phys. B Atom. Mol. Opt. Phys. 22 (1989) 2835]. The time differential perturbed angular correlation method (TDPAC), combined with long-lived positron life time spectroscopy (PLTS), has been used to observe these quantum beats. It is found that the characteristics of the annihilation time distribution are not influenced by the presence of diamagnetic species such as Ar, N₂ and H₂ but are affected by the presence of the paramagnetic O₂ molecule. Our results are encouraging in developing a new method for investigating magnetic fields on an atomic scale.     

Simulation based analysis and an application to an offshore oil and gas production system of the Natvig measures of component importance in repairable systems

In the present paper the Natvig measures of component importance for repairable systems, and its extended version are analyzed for two three-component systems and a bridge system. The measures are also applied to an offshore oil and gas production system. According to the extended version of the Natvig measure a component is important if both by failing it strongly reduces the expected system uptime and by being repaired it strongly reduces the expected system downtime. The results include a study of how different distributions affect the ranking of the components. All numerical results are computed using discrete event simulation. In a companion paper [Huseby AB, Eide KA, Isaksen SL, Natvig B, Gåsemyr, J. Advanced discrete event simulation methods with application to importance measure estimation. 2009, submitted for publication] the advanced simulation methods needed in these calculations are described.