Luca Fiori

Nano-indentation of polymeric surfaces

This paper presents results of normal hardness, plasticity index and elastic modulus for a selection of organic polymers (a poly(methylmethacrylate), PMMA, a poly(styrene), PS, a poly(carbonate), PC, and an ultra-high molecular weight poly(ethylene), UHMWPE) obtained using the contact compliance method. The paper describes in detail the dependence of the imposed penetration depth, the maximum load and the deformation rate upon the hardness and elastic modulus values for these polymeric surfaces; typical penetration depths range from about 10 nm to m where the imposed loads are less than 300 mN. The results show a considerable strain-rate hardening effect for the present systems and possibly a peculiarly harder response of these materials at the near-to-surface (submicron) layers. The paper includes considerations of a practical nature which are drawn in order to overcome some intrinsic limitations of this technique when it is used for polymeric surfaces, especially for a creeping phenomenon which may be observed at the incipient unloading experimental segments. The appropriateness of using a tip calibration constructed upon hard substrates when indenting polymers is reviewed at the conclusion of the paper.

Biomass as an energy source: thermodynamic constraints on the performance of the conversion process.

In the present work an equilibrium model (gas-solid), based on the minimization of the Gibbs energy, has been used in order to estimate the theoretical yield and the equilibrium composition of the reaction products (syngas and char) of biomass thermochemical conversion processes (pyrolysis and gasification). The data obtained from this model have also been used to calculate the heating value of the fuel gas, in order to evaluate the overall energy efficiency of the thermal conversion stage. The proposed model has been applied both to partial oxidation and steam gasification processes with varying air to biomass (ER) and steam to carbon (SC) ratio values and using different feedstocks; the obtained results have been compared with experimental data and with other model predictions obtaining a satisfactory agreement.

Supercritical water gasification of biomass: Thermodynamic constraints.

In the present work, the supercritical water gasification (SCWG) of biomass is analyzed with a view to outlining the possible thermodynamic constraints that must be taken into account to develop this new process. In particular, issues concerning the formation of solid carbon and the process heat duty are discussed. The analysis is conducted by means of a two-phase non-stoichiometric thermodynamic model, based on Gibbs free energy minimization. Results show that char formation at equilibrium only occurs at high biomass concentrations, with a strong dependence on biomass composition. As regards the process heat duty, SCWG is mostly endothermic when biomass concentration is low, although a very small amount of oxidizing agent is able to make the process exothermic, with only a small loss in the heating value of the syngas produced.

Agro-industrial waste to solid biofuel through hydrothermal carbonization

In this paper, the use of grape marc for energy purposes was investigated. Grape marc is a residual lignocellulosic by-product from the winery industry, which is present in every world region where vine-making is addressed. Among the others, hydrothermal carbonization was chosen as a promising alternative thermochemical process, suitable for the treatment of this high moisture substrate. Through a 50 mL experimental apparatus, hydrothermal carbonization tests were performed at several temperatures (namely: 180, 220 and 250 °C) and residence times (1, 3, 8 h). Analyses on both the solid and the gaseous phases obtained downstream of the process were performed. In particular, solid and gas yields versus the process operational conditions were studied and the obtained hydrochar was evaluated in terms of calorific value, elemental analysis, and thermal stability. Data testify that hydrochar form grape marc presents interesting values of HHV (in the range 19.8-24.1 MJ/kg) and physical-chemical characteristics which make hydrochar exploitable as a solid biofuel. In the meanwhile, the amount of gases produced is very small, if compared to other thermochemical processes. This represents an interesting result when considering environmental issues. Statistical analysis of data allows to affirm that, in the chosen range of operational conditions, the process is influenced more by temperature than residence time. These preliminary results support the option of upgrading grape marc toward its energetic valorisation through hydrothermal carbonization.

Supercritical water gasification of biomass for H2 production: Process design

The supercritical water gasification (SCWG) of biomass for H(2) production is analyzed in terms of process development and energetic self-sustainability. The conceptual design of a plant is proposed and the SCWG process involving several substrates (glycerol, microalgae, sewage sludge, grape marc, phenol) is simulated by means of AspenPlus™. The influence of various parameters - biomass concentration and typology, reaction pressure and temperature - is analyzed. The process accounts for the possibility of exploiting the mechanical energy of compressed syngas (later burned to sustain the SCWG reaction) through expansion in turbines, while purified H(2) is fed to fuel cells. Results show that the SCWG reaction can be energetically self-sustained if minimum feed biomass concentrations of 15-25% are adopted. Interestingly, the H(2) yields are found to be maximal at similar feed concentrations. Finally, an energy balance is performed showing that the whole process could provide a net power of about 150 kW(e)/(1000 kg(feed)/h).

Modeling of the devolatilization kinetics during pyrolysis of grape residues.

Thermo-gravimetric analysis (TGA) was performed on grape seeds, skins, stalks, marc, vine-branches, grape seed oil and grape seeds depleted of their oil. The TGA data was modeled through Gaussian, logistic and Miura-Maki distributed activation energy models (DAEMs) and a simpler two-parameter model. All DAEMs allowed an accurate prediction of the TGA data; however, the Miura-Maki model could not account for the complete range of conversion for some substrates, while the Gaussian and logistic DAEMs suffered from the interrelation between the pre-exponential factor k0 and the mean activation energy E0--an obstacle that can be overcome by fixing the value of k0 a priori. The results confirmed the capabilities of DAEMs but also highlighted some drawbacks in their application to certain thermodegradation experimental data.

Hydrothermal carbonization of off-specification compost: A byproduct of the organic municipal solid waste treatment

The possibility to apply the hydrothermal carbonization (HTC) process to off-specification compost (EWC 19.05.03) at present landfilled was investigated in this work. The aim was to produce a carbonaceous solid fuel for energy valorization, with the perspective of using HTC as a complementary technology to common organic waste treatments. Thus, samples of EWC 19.05.03 produced by a composting plant were processed through HTC in a batch reactor. Analytical activities allowed to characterize the HTC products and their yields. The hydrochar was characterized in terms of heating value, thermal stability and C, H, O, N, S and ash content. The liquid phase was characterized in terms of total organic carbon and mineral content. The composition of the gas phase was measured. Results show that the produced hydrochar has a great potentiality for use as solid fuel.

Dynamic surface tension measurements on molten metal-oxygen systems: model validation on molten tin

Abstract A theoretical model on oxygen transport at the surface of liquid metals has been validated by dynamic surface tension measurements performed on liquid tin as test metal. The oxygen contamination conditions have been obtained at different oxygen partial pressures under low total pressure conditions (Knudsen regime), confirming that an oxide removal regime occurs under an oxygen partial pressure much higher than the equilibrium one (the “Effective Oxidation Pressure”). Experimental results are reported which give a new insight on the relative importance of the various processes due to the oxygen mass transport between the liquid metal and the gas phase. The critical aspects involved in surface tension measurements of liquid metals, related to the problem of liquid metal–oxygen interactions, are also carefully underlined.

Grape by-products: extraction of polyphenolic compounds using supercritical CO2 and liquid organic solvent - a preliminary investigation.

This research focussed on the exploitation of grape by-products as a source of polyphenolic compounds, which are of interest to the food, pharmaceutical and cosmetic industries. In particular, two substrates were tested: Pinot Noir grape skins and grape seeds. Pinot Noir grape skins were extracted by supercritical CO2 added with ethanol as modifier at constant temperature (45 °C) and at variable pressure (200, 300, 400 or 500 bar). The supercritical extraction kinetics of polyphenolic compounds was obtained. Grape seeds were extracted by combining supercritical (at 40 °C and 500 bar and using CO2 or CO2 added with ethanol as modifier) with liquid ethanol extraction. The supercritical technique seemed not to be really effective in extracting polyphenolic compounds; it can be anyway utilized to selectively extract grape seed oil by avoiding any solvent contamination of the matrix which can be further extracted for the recovery of polyphenolic compounds by means of liquid organic solvent.

Lipid profiles of oil from trout (Oncorhynchus mykiss) heads, spines and viscera: Trout by-products as a possible source of omega-3 lipids?

Lipid profiles of fish oil extracted from trout heads, spines and viscera using supercritical carbon dioxide and Randall extraction with hexane were measured. The amount of unsaturated fatty acids (as a percentage of total fatty acids) was within the range of 72.6-75.3% in all the substrates. A significant presence of the most important omega-3 fatty acids was detected. Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) content in oil from spines, heads and viscera resulted to be 8.7% and 7.3%, 7.9% and 6.3%, and 6.4% and 6.0%, respectively. A low (≈3%), but worth noting, presence of lipids with omega-1 polyunsaturated fatty chains was observed in all the oils. Finally, significant differences were noticed in the relative amounts of triacylglycerides (TAG), diacylglycerides (DAG) and free fatty acids (FFA). Whereas oil from heads and spines was essentially composed of TAG (≈98%), in viscera oil the molar distribution ratio became TAG:DAG:FFA=87:8:5.