Asphalt rubber mixtures with warm mix asphalt additives

En los últimos años, debido a la creciente preocupación por el calentamiento global y el cambio climático, uno de los retos más importantes a los que se enfrenta nuestra sociedad es el uso eficiente y económico de energía así como la necesidad correspondiente de reducir los gases de efecto invernadero (GEI). Las tecnologías de mezclas semicalientes se han convertido en un nuevo e importante tema de investigación en el campo de los materiales para pavimentos ya que ofrece una solución potencial para la reducción del consumo energético y las emisiones de GEI durante la producción y puesta en obra de las mezclas bituminosas. Por otro lado, los pavimentos que contienen polvo de caucho procedente de neumático fuera de uso, al hacer uso productos de desecho, ahorran energía y recursos naturales. Estos pavimentos ofrecen una resistencia mejorada a la formación de roderas, a la fatiga y a la fisuración térmica, reducen los costes de mantenimiento y el ruido del tráfico así como prolongan la vida útil del pavimento. Sin embargo, estas mezclas presentan un importante inconveniente: la temperatura de fabricación se debe aumentar en comparación con las mezclas asfálticas convencionales, ya que la incorporación de caucho aumenta la viscosidad del ligante y, por lo tanto, se producen mayores cantidades de emisiones de GEI. En la presente Tesis, la tecnología de mezclas semicalientes con aditivos orgánicos (Sasobit, Asphaltan A, Asphaltan B, Licomont) se incorporó a la de betunes de alta viscosidad modificados con caucho (15% y 20% de caucho) con la finalidad de dar una solución a los inconvenientes de mezclas con caucho gracias a la utilización de aditivos reductores de la viscosidad. Para este fin, se estudió si sería posible obtener una producción más sostenible de mezclas con betunes de alto contenido en caucho sin afectar significativamente su nivel de rendimiento mecánico. La metodología aplicada para evaluar y comparar las características de las mezclas consistió en la realización de una serie de ensayos de laboratorio para betunes y mezclas con caucho y con aditivos de mezclas semicalientes y de un análisis del ciclo de vida híbrido de la producción de mezclas semicalientes teniendo en cuenta la papel del aditivo en la cadena de suministro con el fin de cuantificar con precisión los beneficios de esta tecnología. Los resultados del estudio indicaron que la incorporación de los aditivos permite reducir la viscosidad de los ligantes y, en consecuencia, las temperaturas de producción y de compactación de las mezclas. Por otro lado, aunque la adición de caucho mejoró significativamente el comportamiento mecánico de los ligantes a baja temperatura reduciendo la susceptibilidad al fenómeno de fisuración térmica, la adición de las ceras aumentó ligeramente la rigidez. Los resultados del estudio reológico mostraron que la adición de porcentajes crecientes de caucho mejoraban la resistencia del pavimento con respecto a la resistencia a la deformación permanente a altas temperaturas y a la fisuración térmica a bajas temperaturas. Además, se observó que los aditivos mejoran la resistencia a roderas y la elasticidad del pavimento al aumentar el módulo complejo a altas temperaturas y al disminuir del ángulo de fase. Por otra parte, el estudio reológico confirmó que los aditivos estudiados aumentan ligeramente la rigidez a bajas temperaturas. Los ensayos de fluencia llevados a cabo con el reómetro demostraron una vez más la mejora en la elasticidad y en la resistencia a la deformación permanente dada por la adición de las ceras. El estudio de mezclas con caucho y aditivos de mezclas semicalientes llevado a cabo demostró que las temperaturas de producción/compactación se pueden disminuir, que las mezclas no experimentarían escurrimiento, que los aditivos no cambian significativamente la resistencia conservada y que cumplen la sensibilidad al agua exigida. Además, los aditivos aumentaron el módulo de rigidez en algunos casos y mejoraron significativamente la resistencia a la deformación permanente. Asimismo, a excepción de uno de los aditivos, las mezclas con ceras tenían la misma o mayor resistencia a la fatiga en comparación con la mezcla control. Los resultados del análisis de ciclo de vida híbrido mostraron que la tecnología de mezclas semicalientes es capaz de ahorrar significativamente energía y reducir las emisiones de GEI, hasta un 18% y 20% respectivamente, en comparación con las mezclas de control. Sin embargo, en algunos de los casos estudiados, debido a la presencia de la cera, la temperatura de fabricación debe reducirse en un promedio de 8 ºC antes de que los beneficios de la reducción de emisiones y el consumo de combustible puedan ser obtenidos. Los principales sectores contribuyentes a los impactos ambientales generados en la fabricación de mezclas semicalientes fueron el sector de los combustibles, el de la minería y el de la construcción. Due to growing concerns over global warming and climate change in recent years, one of the most important challenges facing our society is the efficient and economic use of energy, and with it, the corresponding need to reduce greenhouse gas (GHG) emissions. The Warm Mix Asphalt (WMA) technology has become an important new research topic in the field of pavement materials as it offers a potential solution for the reduction of energy consumption and GHG emissions during the production and placement of asphalt mixtures. On the other hand, pavements containing crumb-rubber modified (CRM) binders save energy and natural resources by making use of waste products. These pavements offer an improved resistance to rutting, fatigue and thermal cracking; reduce traffic noise and maintenance costs and prolong pavement life. These mixtures, however, present one major drawback: the manufacturing temperature is higher compared to conventional asphalt mixtures as the rubber lends greater viscosity to the binder and, therefore, larger amounts of GHG emissions are produced. In this dissertation the WMA technology with organic additives (Sasobit, Asphaltan A, Asphaltan B and Licomont) was applied to CRM binders (15% and 20% of rubber) in order to offer a solution to the drawbacks of asphalt rubber (AR) mixtures thanks to the use of fluidifying additives. For this purpose, this study sought to determine if a more sustainable production of AR mixtures could be obtained without significantly affecting their level of mechanical performance. The methodology applied in order to evaluate and compare the performance of the mixtures consisted of carrying out several laboratory tests for the CRM binders and AR mixtures with WMA additives (AR-WMA mixtures) and a hybrid input-output-based life cycle assessment (hLCA) of the production of WMA. The results of the study indicated that the incorporation of the organic additives were able to reduce the viscosity of the binders and, consequently, the production and compaction temperatures. On the other hand, although the addition of rubber significantly improved the mechanical behaviour of the binders at low temperatures reducing the susceptibility to thermal cracking phenomena, the addition of the waxes slightly increased the stiffness. Master curves showed that the addition of increasing percentages of rubber improved the resistance of the pavement regarding both resistance to permanent deformation at high temperatures and thermal cracking at low temperatures. In addition, the waxes improved the rutting resistance and the elasticity as they increased the complex modulus at high temperatures and decreased the phase angle. Moreover, master curves also attest that the WMA additives studied increase the stiffness at low temperatures. The creep tests carried out proved once again the improvement in the elasticity and in the resistance to permanent deformation given by the addition of the waxes. The AR-WMA mixtures studied have shown that the production/compaction temperatures can be decreased, that the mixtures would not experience binder drainage, that the additives did not significantly change the retained resistance and fulfilled the water sensitivity required. Furthermore, the additives increased the stiffness modulus in some cases and significantly improved the permanent deformation resistance. Except for one of the additives, the waxes had the same or higher fatigue resistance compared to the control mixture. The results of the hLCA demonstrated that the WMA technology is able to significantly save energy and reduce GHG emissions, up to 18% and 20%, respectively, compared to the control mixtures. However, in some of the case studies, due to the presence of wax, the manufacturing temperature at the asphalt plant must be reduced by an average of 8ºC before the benefits of reduced emissions and fuel usage can be obtained. The results regarding the overall impacts generated using a detailed production layer decomposition indicated that fuel, mining and construction sectors are the main contributors to the environmental impacts of manufacturing WMA mixtures.

Simultaneous determination of multiclass emerging contaminants in aquatic plants by ultrasound assisted matrix solid phase dispersion and GC-MS

A multiresidue method was developed for the simultaneous determination of 31 emerging contaminants (pharmaceutical compounds, hormones, personal care products, biocides and flame retardants) in aquatic plants. Analytes were extracted by ultrasound assisted-matrix solid phase dispersion (UA-MSPD) and determined by gas chromatography-mass spectrometry after sylilation. The method was validated for different aquatic plants (Typha angustifolia, Arundo donax and Lemna minor) and a semiaquatic cultivated plant (Oryza sativa) with good recoveries at concentrations of 100 and 25 ng g-1 wet weight, ranging from 70 to 120 %, and low method detection limits (0.3 to 2.2 ng g-1 wet weight). A significant difference of the chromatographic response was observed for some compounds in neat solvent versus matrix extracts and therefore quantification was carried out using matrix-matched standards in order to overcome this matrix effect. Aquatic plants taken from rivers located at three Spanish regions were analyzed and the compounds detected were parabens, bisphenol A, benzophenone-3, cyfluthrin and cypermethrin. The levels found ranged from 6 to 25 ng g-1 wet weight except for cypermethrin that was detected at 235 ng g-1 wet weight in Oryza sativa samples.

Potential effects of gas hydrate on human welfare

For almost 30 years. serious interest has been directed toward natural gas hydrate, a crystalline solid composed of water and methane, as a potential (i) energy resource, (ii) factor in global climate change, and (iii) submarine geohazard. Although each of these issues can affect human welfare, only (iii) is considered to be of immediate importance. Assessments of gas hydrate as an energy resource have often been overly optimistic, based in part on its very high methane content and on its worldwide occurrence in continental margins. Although these attributes are attractive, geologic settings, reservoir properties, and phase-equilibria considerations diminish the energy resource potential of natural gas hydrate. The possible role of gas hydrate in global climate change has been often overstated. Although methane is a “greenhouse” gas in the atmosphere, much methane from dissociated gas hydrate may never reach the atmosphere, but rather may be converted to carbon dioxide and sequestered by the hydrosphere/biosphere before reaching the atmosphere. Thus, methane from gas hydrate may have little opportunity to affect global climate change. However, submarine geohazards (such as sediment instabilities and slope failures on local and regional scales, leading to debris flows, slumps, slides, and possible tsunamis) caused by gas-hydrate dissociation are of immediate and increasing importance as humankind moves to exploit seabed resources in ever-deepening waters of coastal oceans. The vulnerability of gas hydrate to temperature and sea level changes enhances the instability of deep-water oceanic sediments, and thus human activities and installations in this setting can be affected.

Caught in the act: gas and stellar velocity dispersions in a fast Quenching compact star-forming galaxy at z ~ 1.7

We present Keck I MOSFIRE spectroscopy in the Y and H bands of GDN-8231, a massive, compact, star-forming galaxy at a redshift of z ~ 1.7. Its spectrum reveals both Hα and [Nii] emission lines and strong Balmer absorption lines. The Hα and Spitzer MIPS 24 μm fluxes are both weak, thus indicating a low star-formation rate of SFR≲5-10 M_⨀ yr−1. This, added to a relatively young age of ~700 Myr measured from the absorption lines, provides the first direct evidence for a distant galaxy being caught in the act of rapidly shutting down its star formation. Such quenching allows GDN-8231 to become a compact, quiescent galaxy, similar to three other galaxies in our sample, by z ~ 1.5. Moreover, the color profile of GDN-8231 shows a bluer center, consistent with the predictions of recent simulations for an early phase of inside-out quenching. Its line-of-sight velocity dispersion for the gas, σ_LOG^gas = 127 ± 32 km s^−1, is nearly 40% smaller than that of its stars, σ_LOG^* = 215 ± 35 km s^−1. High-resolution hydro-simulations of galaxies explain such apparently colder gas kinematics of up to a factor of ~1.5 with rotating disks being viewed at different inclinations and/or centrally concentrated star-forming regions. A clear prediction is that their compact, quiescent descendants preserve some remnant rotation from their star-forming progenitors.

Evidence of Intracrystalline Mesostructured Porosity in Zeolites by Advanced Gas Sorption, Electron Tomography and Rotation Electron Diffraction

The small size of micropores (typically <1 nm) in zeolites causes slow diffusion of reactant and product molecules in and out of the pores and negatively impacts the product selectivity of zeolite based catalysts, for example, fluid catalytic cracking (FCC) catalysts. Size-tailored mesoporosity was introduced into commercial zeolite Y crystals by a simple surfactant-templating post-synthetic mesostructuring process. The resulting mesoporous zeolite Y showed significantly improved product selectivity in both laboratory testing and refinery trials. Advanced characterization techniques such as electron tomography, three-dimensional rotation electron diffraction, and high resolution gas adsorption coupled with hysteresis scanning and density functional theory, unambiguously revealed the intracystalline nature and connectivity of the introduced mesopores. They can be considered as molecular highways that help reactant and product molecules diffuse quickly to and away from the catalytically active sites within the zeolite crystals and, thus, shift the selectivity to favor the production of more of the valuable liquid fuels at reduced yields of coke and unconverted feed.

Study of the emissions from pyrolytic and oxidative thermal decomposition of PVC

Polyvinyl chloride (PVC) is one of the plastics most extensively used due to its versatility. The demand of PVC resin in Europe during 2012 reached 5000 ktonnes1. PVC waste management is a big problem because of the high volume generated all over the world and its chlorine content. End-of-life PVC is mainly mixed with municipal solid waste (MSW) and one common disposal option for this is waste-to-energy incineration (WtE). The presence of plastics such as PVC in the fuel mix increases the heating value of the fuel. PVC has two times higher energy content than MSW ‒around 20 MJ/kg vs 10 MJ/kg, respectively. However, the high chlorine content in PVC resin, 57 wt.%, may be a source for the formation of hazardous chlorinated organic pollutants in thermal processes. Chlorine present in the feedstock of WtE plants plays an important role in the formation of (i) chlorine (Cl2) and (ii) hydrochloric gas (HCl), both of them responsible for corrosion, and (iii) chlorinated organic pollutants2. In this work, pyrolytic and oxidative thermal degradation of PVC resin were carried out in a laboratory scale reactor at 500 ºC in order to analyze the influence of the reaction atmosphere on the emissions evolved. Special emphasis was put on the analysis of chlorinated organic pollutants such as polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and other related compounds like polychlorobenzenes (PCBzs), polychlorophenols (PCPhs) and polycyclic aromatic hydrocarbons (PAHs). Another objective of this work was to compare the results with those of a previous work3 in which emissions at different temperatures in both pyrolysis and combustion of another PVC resin had been studied; in that case, experiments for PCDD/Fs emissions had been performed only at 850 ºC.

Orbital phase-resolved spectroscopy of 4U 1538−52 with MAXI

Context. 4U 1538−52, an absorbed high mass X-ray binary with an orbital period of ~3.73 days, shows moderate orbital intensity modulations with a low level of counts during the eclipse. Several models have been proposed to explain the accretion at different orbital phases by a spherically symmetric stellar wind from the companion. Aims. The aim of this work is to study both the light curve and orbital phase spectroscopy of this source in the long term. In particular, we study the folded light curve and the changes in the spectral parameters with orbital phase to analyse the stellar wind of QV Nor, the mass donor of this binary system. Methods. We used all the observations made from the Gas Slit Camera on board MAXI of 4U 1538−52 covering many orbits continuously. We obtained the good interval times for all orbital phase ranges, which were the input for extracting our data. We estimated the orbital period of the system and then folded the light curves, and we fitted the X-ray spectra with the same model for every orbital phase spectrum. We also extracted the averaged spectrum of all the MAXI data available. Results. The MAXI spectra in the 2–20 keV energy range were fitted with an absorbed Comptonisation of cool photons on hot electrons. We found a strong orbital dependence of the absorption column density but neither the fluorescence iron emission line nor low energy excess were needed to fit the MAXI spectra. The variation in the spectral parameters over the binary orbit were used to examine the mode of accretion onto the neutron star in 4U 1538−52. We deduce a best value of Ṁ/v∞ = 0.65 × 10-9M⊙ yr-1/ (km s-1) for QV Nor.

X lberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design (EQUIFASE): June 28-July 1, 2015 - Alicante (Spain): Book of Abstracts

The general purpose of the EQUIFASE Conference is to promote the Scientific and Technologic exchange between people from both the academic and the industrial environment in the field of Phase Equilibria and Thermodynamic Properties for the Design of Chemical Processes. Topics: Measurement of Thermodynamic Properties. Phase Equilibria and Chemical Equilibria. Theory and Modelling. Alternative Solvents. Supercritical Fluids. Ionic Liquids. Energy. Gas and oil. Petrochemicals. Environment and sustainability. Biomolecules and Biotechnology. Product and Process Design. Databases and Software. Education.

The eastern ‘partnership’ of gas. Gazprom and CNPC strike a deal on gas supplies to China. OSW COMMENTARY No. 139, 2014-06-16

The CEOs of Gazprom and China’s CNPC signed a contract concerning Russian gas supplies to China on 21 May 2014 in Shanghai. The contract had been under negotiation for many years and was signed in the presence of the two countries’ presidents. Under this 30-year deal, ultimately 38 billion m3 of natural gas will be exported annually from eastern Siberian fields (Chayandinskoye and Kovyktinskoye) via the Power of Siberia pipeline planned for construction in 2015–2019. The lengthy negotiation process (initial talks regarding this issue began back in the 1990s), the circumstances surrounding the signing of the contract (it was signed only on the second day of Vladimir Putin’s visit to Shanghai, and the Russian president’s personal engagement in the final phase of the talks turned out to be a key element) and information concerning the provisions of the contract (the clause determining the contract price has not been revealed) all indicate that the terms of the compromise are more favourable for China than for Russia. This contract is at present important to Russia mainly for political reasons (it will use the future diversification of gas export routes as an instrument in negotiations with the EU). However, the impact of this instrument seems to be limited since supplies cannot be redirected from Europe to Asia. It is unclear whether the contract will bring the anticipated long-term economic benefits to Gazprom. The gas price is likely to remain at a level of between US$350 and US$390 per 1000 m3. Given the high costs of gas field operation and production and transport infrastructure development, this may mean that supplies will be carried out at the margin of profitability. The Shanghai contract does not conclude the negotiation process since a legally binding agreement on gas pipeline construction has not been signed and not all of the financial aspects of the project have been agreed upon as yet (such as the issue of possible Chinese prepayments for gas supplies).

Designing biostable polyurethane elastomers for biomedical implants

The chemical structure, synthesis, morphology, and properties of polyurethane elastomers are briefly discussed. The current understanding of the effect of chemical structure and the associated morphology on the stability of polyurethanes in the biological environments is reviewed. The degradation of conventional polyurethanes appears as surface or deep cracking, stiffening, and deterioration of mechanical properties, such as flex-fatigue resistance. Polyester and poly( tetramethylene oxide) based polyurethanes degrade by hydrolytic and oxidative degradation of ester and ether functional groups, respectively. The recent approaches to develop polyurethanes with improved long-term biostability are based on developing novel polyether, hydrocarbon, polycarbonate, and siloxane macrodiols to replace degradation-prone polyester and polyether macrodiols in polyurethane formulations. The new approaches are discussed with respect to synthesis, properties and biostability based on reported in vivo studies. Among the newly developed materials, siloxane-based polyurethanes have exhibited excellent biostability and are expected to find many applications in biomedical implants.

Damage by eutectic particle cracking in aluminum casting alloys A356/357

The strain dependence of particle cracking in aluminum alloys A356/357 in the T6 temper has been studied in a range of microstructures produced by varying solidification rate and Mg content, and by chemical (Sr) modification of the eutectic silicon. The damage accumulates linearly with the applied strain for all microstructures, but the rate depends on the secondary dendrite arm spacing and modification state. Large and elongated eutectic silicon particles in the unmodified alloys and large pi-phase (Al9FeMg3Si5) particles in alloy A357 show the greatest tendency to cracking. In alloy A356, cracking of eutectic silicon particles dominates the accumulation of damage while cracking of Fe-rich particles is relatively unimportant. However, in alloy A357, especially with Sr modification, cracking of the large pi-phase intermetallics accounts for the majority of damage at low and intermediate strains but becomes comparable with silicon particle cracking at large strains. Fracture occurs when the volume fraction of cracked particles (eutectic silicon and Fe-rich intermetallics combined) approximates 45 pct of the total particle volume fraction or when the number fraction of cracked particles is about 20 pct. The results are discussed in terms of Weibull statistics and existing models for dispersion hardening.

Effects of adsorbed phase on diffusion of subcritical hydrocarbons in activated carbon at low pressures

Diffusions of free and adsorbed molecules of subcritical hydrocarbons in activated carbon were investigated to study the influence of adsorbed molecules on both diffusion processes at low pressures. A collision reflection factor, defined as the fraction of molecules undergoing collision to the solid surface over reflection from the surface, is incorporated into Knudsen diffusivity and surface diffusivity in meso/macropores. Since the porous structure of activated carbon is bimodal in nature, the diffusion of adsorbed molecules is contributed by that of weakly adsorbed molecules on the meso/macropore surfaces and that of strongly adsorbed molecules in the small confinement of micropores. The mobility of adsorbed molecules on the meso/macropore surface is characterized by the surface diffusivity D-mu 2, while that in the micropore is characterized by D-mu 1. In our study with subcritical hydrocarbons, we have found that the former increases almost linearly with pressure, while the latter exhibits a sharp increase at a very low-pressure region and then decreases beyond a critical pressure. This critical pressure is identified as a pressure at which the micropores are saturated.

Adsorption of pure fluids in activated carbon with a modified lattice gas model

In this article we study the effects of adsorbed phase compression, lattice structure, and pore size distribution on the analysis of adsorption in microporous activated carbon. The lattice gas approach of Ono-Kondo is modified to account for the above effects. Data of nitrogen adsorption at 77 K onto a number of activated carbon samples are analyzed to investigate the pore filling pressure versus pore width, the packing effect, and the compression of the adsorbed phase. It is found that the PSDs obtained from this analysis are comparable to those obtained by the DFT method. The discrete nature of the PSDs derived from the modified lattice gas theory is due to the inherent assumption of discrete layers of molecules. Nevertheless, it does provide interesting information on the evolution of micropores during the activation process.

Atom probe field ion microscope measurements of carbon segregation at an a:a grain boundary and service failures by intergranular stress corrosion cracking

This work reports on a critical measurement to understand the intergranular stress corrosion cracking (IGSCC) of pipeline steels: the atom probe field ion microscope (APFIM) measurement of the carbon concentration at a grain boundary (GB). The APFIM measurement was related to the microstructure and to IGSCC observations. The APFIM indicated that the GB carbon concentration of X70 was similar to 10 at% or less, which correlated with a high resistance to IGSCC for X70. (C) 2005 Elsevier Ltd. All rights reserved.

Hydrodynamics and mass transfer coefficient in three-phase air-lift reactors containing activated sludge

This study was to investigate the impacts of operating conditions and liquid properties on the hydrodynamics and volumetric mass transfer coefficient in activated sludge air-lift reactors. Experiments were conducted in internal and external air-lift reactors. The activated sludge liquid displayed a non-Newtonian rheological behavior. With an increase in the superficial gas velocity, the liquid circulation velocity, gas holdup and mass transfer coefficient increased, and the gas residence time decreased. The liquid circulation velocity, gas holdup and the mass transfer coefficient decreased as the sludge loading increased. The flow regime in the activated sludge air-lift reactors had significant effect on the liquid circulation velocity and the gas holdup, but appeared to have little impact on the mass transfer coefficient. The experimental results in this study were best described by the empirical models, in which the reactor geometry, superficial gas velocity and/or power consumption unit, and solid and fluid properties were employed. (c) 2006 Elsevier B.V. All rights reserved.