An Inverse Problem for a Nonlinear Diffusion-Convection Equation

A method for constructing the Dirichlet-to-Neumann map for a nonlinear diffusion-convection equation is presented. The problem is reduced to the solution of a nonlinear integral equation in one independent variable. Existence and uniqueness of the solution may be proven for small times via a contraction mapping technique.     

Crystallization kinetics of virgin and processed poly(lactic acid)

Poly(lactic acid) (PLA) is an emerging material mainly because it can be synthesized from renewable resources and is thus environmentally and ecologically safe. The mechanical properties, above all the thermal resistance of PLA are determined by the crystalline content: the heat deflection temperature of crystalline PLA can reach 100 °C, whereas amorphous PLA loses mechanical properties at temperatures slightly higher than 60 °C. However, PLA has a low crystallization rate, so that after processing it remains mostly amorphous. This characteristic heavily limits the use of PLA for commercial applications. Many studies have been recently published on the crystallization kinetics of PLA. The effect of processing on this feature is however often neglected. In this work, the significance of processing on the crystallization kinetics of a commercial PLA was investigated. Two processing methods were explored: extrusion and injection moulding. The obtained materials, and the starting pellets of virgin polymer, were analyzed by calorimetry in order to obtain the crystallization kinetics. Two protocols were adopted to determine the crystallization rates during cooling from the melt or heating from the solid. The parameters of a kinetic equation were determined for all the materials and protocols adopted and it was thus possible to describe the evolution of crystallinity during heating and during cooling.     

A new crystal form of the NSAID dexketoprofen

Dexketoprofen [(2S)‐2‐(3‐benzoylphenyl)propanoic acid], C₁₆H₁₄O₃, is the S‐enantiomer of ketoprofen, a nonsteroidal anti‐inflammatory drug (NSAID) that has analgesic, antipyretic and anti‐inflammatory properties, and finds applications for the short‐term treatment of mild to moderate pain. A new crystalline phase of dexketoprofen is reported. Its solid‐state structure was determined by single‐crystal X‐ray diffraction (SCXRD). The molecular structure of the two independent molecules found in the asymmetric unit of this new phase ( DXKP‐β ) were compared to those of the already known crystal form of dexketoprofen ( DXKP‐α ) and with the S‐enantiomer of the racemic compound. The three different conformers of dexketoprofen found in DXKP‐α and DXKP‐β were then investigated by computational methods. The optimized structures are very close to the corresponding starting geometries and do not differ significantly in energy. The crystal packing of DXKP‐β was studied by means of Hirshfeld surface (HS) analysis; interaction energies were also calculated. A comparison with DXKP‐α shows close similarities between the two crystal forms, i.e. in both cases, molecules assemble through the catemer O—H…O synthon of the carboxylic acid stabilized by additional C—H…O contacts and, accordingly, the interaction energies, as well as the contributions to the HS area, are very similar. Finally, the thermal behaviour of the two polymorphs of dexketoprofen was assessed by means of XRD (both from single crystal and microcrystalline powder) and differential scanning calorimetry (DSC); both crystal forms are stable under the experimental conditions adopted (air, 300–350 K for DXKP‐α and 300–340 K DXKP‐β ) and no solid–solid phase transition occurs between the two crystal forms in the investigated temperature range (from 100 K up to ca 350 K).     

Influence of water addition on MILD ammonia combustion performances and emissions

The global energy shift towards the exploitation of Renewable Energy Sources requires the development of proper energy storage and back-up technologies to deal with their intermittency and seasonality. Renewable Energy chemical storage offers the possibility of efficiently storing large amounts of energy for long time. On the other hand, ammonia is increasingly considered a feasible alternative to the use of hydrogen, due to the existence of already well assessed production technologies and transport infrastructures. However, the exploitation of ammonia as an energy carrier poses some relevant challenges. The most relevant ones concern combustion stability and NO_x emissions, when ammonia is burned in traditional conditions. A promising approach to ensure combustion stability while containing NO_x emissions relies on the shift from traditional to new combustion modes. MILD Combustion has been proven as a reliable alternative to reach these targets. At the same time, water addition to reactants is a well-known strategy that promote DeNO_x routes in fossil fuel combustion.In this work, combustion of ammonia-air mixtures assisted by water is studied in a cyclonic burner exercised under MILD operative conditions, to evaluate the effect of water addition on NO_x emissions and process stability. The analyses were carried out in premixed and non-premixed feeding conditions.Results highlighted that water addition to the reactant mixture may represent a very simple and efficient solution in determining the reduction of NO_x emissions in ammonia combustion, especially in fuel-lean conditions.Moreover, the comparison between premixed and non-premixed configuration shows that it is possible to enhance the process performance through a simultaneous optimization of the burner internal flow-field and reactants injection strategies.     

Polymorphism and Thermal Behaviour of Syndiotactic Poly(propylene)/Carbon Nanotube Composites

Summary: Nanocomposite materials were obtained by blending multi‐wall carbon nanotubes (CN), obtained by acetylene catalytic chemical vapour deposition (CVD) on Co/Fe‐modified NaY zeolite, with syndiotactic poly(propylene) (sPP). The nanotubes, well dispersed in the polymer matrix, favour the crystallization of the sPP helical chains and significantly improve the sPP thermal stability either in nitrogen or in air. The morphology of the sPP affects the behaviour of the sPP degradation in air.

Thermogravimetric analysis in air of pure sPP and the nanocomposite material.     

Pressure-dependent viscosity and free volume of atactic and syndiotactic polystyrene

The effect of pressure on viscosity is an important but often overlooked aspect of the flow properties of polymeric materials. In this work, two polymers (an atactic and a syndiotactic Polystyrene) were characterized to determine the effect of pressure on viscosity. In particular, a device was adopted to increase the exit pressure of a standard capillary rheometer, thus obtaining data of viscosity under high pressure and high shear rates. The Simha-Somcynsky equation of state was applied to the pressure–volume–temperature experimental data of both materials to obtain the dependence of free volume on temperature and pressure. The Doolittle equation was eventually employed to verify the dependence of viscosity on free volume. It was found that, for both materials, a linear relationship holds between the logarithm of zero-shear-rate viscosity (at several temperatures and pressures) and the inverse of free volume.     

Fuel and thermal load flexibility of a MILD burner

The strategy to stabilize distributed combustion regimes adopting cyclonic flow fields has been proven to be challenging. In fact, the establishment of a toroidal flow field within a combustion chamber may ensure the recirculation of mass and sensible enthalpy required to simultaneously dilute the fresh reactants and increase the temperature above the autoignition one. The combination of reactants dilution and preheating may greatly increase system energy efficiency and lower pollutants production producing very peculiar combustion regime (named MILD Combustion). At the same time this strategy can be compromised if the sensible enthalpy is not high enough to promote the auto-ignition process of diluted mixtures. This may happen either because of an inefficient recirculation system or due to a too low calorific fuel. The paper aims at exploiting the performance of a small-size cyclonic burner for a conventional fuel (CH₄) and a low calorific fuel (synthetic biogas) through the characterization of the process stabilization and pollutant emissions as a function of the mixture equivalence ratio and the nominal thermal power of the inlet mixture (from 2 to 10?kW), with the aim of identifying the optimal operating condition of the system. Results suggest that the system has to be exercised with mixtures with compositions slightly under the stoichiometric conditions and in a well identified temperature range to minimize both NO_x and CO emission. The burner can be easily exercised also with low calorific fuels for higher thermal powers according to the low LHV. However, it results that an efficient recirculation of the exhausts produces a robust MILD combustion condition also when low calorific fuels are used.     

Progress towards an unassisted element identification from Laser Induced Breakdown Spectra with automatic ranking techniques inspired by text retrieval

In this communication, we will illustrate an algorithm for automatic element identification in LIBS spectra which takes inspiration from the vector space model applied to text retrieval techniques. The vector space model prescribes that text documents and text queries are represented as vectors of weighted terms (words). Document ranking, with respect to relevance to a query, is obtained by comparing the vectors representing the documents with the vector representing the query.     

The Effect of Diluent on the Sustainability of MILD Combustion in a Cyclonic Burner

The present study investigates the characteristics of MILD/flameless combustion in a cyclonic lab-scale burner. Such a configuration is effective for achieving turbulent mixing in a very short time while allowing for a reasonably long residence time for the development of combustion reactions. These two constraints are mandatory in the case of MILD combustion processes (high inlet temperatures and diluted mixtures). Such operating conditions are achieved through massive heat/mass recirculation towards the fresh incoming mixtures by recycling the exhausted gases, featuring a process where chemical kinetics times are elongated because of the dilution levels. Thus, long residence times are needed to achieve a satisfying reaction progress, and the high inlet temperatures result in fast and efficient mixing between disproportionate flows to avoid the onset of oxidation reactions before achieving diluted conditions. Under these constraints, a lab-scale facility was designed and built. The oxidation processes of C₃H₈/O₂ mixtures highly diluted in N₂ or CO₂ were investigated by varying the external parameters of the system, namely, the inlet temperature (up to 1300 K) and the mixture composition (from lean to rich mixtures). Several combustion regimes were experimentally identified. When the MILD regime was established, the combustion process became homogeneous within the burner without luminous emissions. To investigate the distributed nature of the MILD combustion processes, chemical simulations were performed under the assumption of a well-stirred reactor. For both the diluents, good agreement between the experimental and numerical results was obtained for MILD combustion conditions.     

H2O and CO2 Dilution in MILD Combustion of Simple Hydrocarbons

MILD combustion is a very attractive technology because of its intrinsic features for energy production from diluted gas deriving from bio- or thermochemical degradation of biomass. An effective use of such a technology for diluted fuel requires a thorough analysis of ignition and oxidation behavior to highlight the potential effects of the different fuel components on the basis of temperature and diluent/oxygen/fuel mixture composition. In this work, ignition and oxidation of a model gas surrogate for the gaseous fraction of biomass pyrolysis products containing C₁-C₂ species, CO and CO₂ were experimentally and numerically studied over a wide range of temperature and overall composition in the presence of large amounts of CO₂ or H₂O. Experimental results showed that such species significantly alter the evolution of the ignition process in dependence on temperature range and mixture composition. Several kinetic models were tested to simulate experimental results. Significant discrepancies occur, especially in the case of steam dilution. Numerical analyses suggested that such diluents acted mainly as third body species at low temperatures, conditioning both radical production pathways and the relative weight of C₁ oxidation/recombination routes, while strongly interacting with the H₂/O₂ high temperature branching mechanisms at high temperatures. Further analyses are mandatory to improve the predictability of the models and extend the applicability of the chemical schemes to non-standard conditions.