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International audience; Cyclohexane oxidation chemistry was investigated using a near-atmospheric pressure JSR at 570 K and ϕ = 0.8. Numerous intermediates including hydroperoxides and highly oxygenated molecules were detected using synchrotron vacuum ultraviolet photoelectron photoion coincidence spectroscopy. Supported by high-level quantum calculations the analysis of photoelectron spectra allowed the firm identification of molecular species formed during the oxidation of cyclohexane. Besides, this work validates recently published gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry data. Unambiguous detection of characteristic hydroperoxides (e.g. γ-ketohydroperoxides) and their respective decomposition products provide support for the conventional O2-addition channels up to the third addition and their relative contribution to the cyclohexane oxidation.The results were also compared to the predictions of a recently proposed new detailed kinetic model of cyclohexane oxidation. Most of the predictions are in line with the current experimental findings highlighting the robustness of the kinetic model. However, the analysis of the recorded slow photoelectron spectra indicating the possible presence of C5 species in the kinetic model provides hints that substituted cyclopentyl radicals from cyclohexyl ring opening might play a minor role in cyclohexane oxidation. Potentially important missing reaction are discussed.

International audience; Cyclic Ethers (CEs) belong to a class of compounds of importance to understand the chemistry of both the engine auto-ignition of hydrocarbon fuels and the combustion of oxygenated biofuels. This article, divided in six parts, aims at systematically analyzing how up-to-date experimental and theoretical methods were applied to unveil the gas-phase oxidation chemistry of these compounds. The first part gives a brief overview on the significance of CEs as intermediates formed during alkane low-temperature oxidation summarizing its generally accepted chemical mechanism. This part also addresses the role of CEs as potential biofuels derived from lignocellulosic biomass and discusses the production methods of these molecules and their combustion performances in engine. The second part presents the different theoretical methods dedicated to calculate the electronic structure, thermochemical and kinetic data of CEs. The third part introduces the experimental methods used in studies related to CEs with a special focus on mass spectrometry and gas chromatography. The fourth part reviews the experimental and modeling studies related to CE formation during the low-temperature oxidation of linear, branched, cyclic alkanes, alkylbenzenes, olefins, and oxygenated fuels. The fifth part analyses the published work concerning the CE degradation chemistry and highlights the dominant involved reactions. To finish, the sixth part concludes and proposes future research directions.

International audience; tert-Butyl hydroperoxide (tBuOOH) is a common intermediate in the oxidation of organic compounds that needs to be accurately quantified in complex gas mixtures for the development of chemical kinetic models of low temperature combustion. This work presents a combined theoretical and experimental investigation on the synchrotron-based VUV single photon ionization of gas-phase tBuOOH in the 9.0 - 11.0 eV energy range, including dissociative ionization processes. Computations consist of the determination of the structures, vibrational frequencies and the energetics of neutral and ionic tBuOOH. The Franck–Condon spectrum for the tBuOOH+ (X+) + e− ← tBuOOH (X) + hν transition is computed, where special treatment is undertaken because of the flexibility of tBuOOH, in particular regarding the OOH group. Through comparison of the experimental mass-selected threshold photoelectron spectra with explicitly correlated coupled cluster calculations and Franck–Condon simulations that account for the flexibility of the molecule, an estimation of the ionization energy is given. The appearance energy of the only fragment observed within the above-mentioned energy range, identified as the tert-butyl C4H9+, is also reported. Finally, the signal branching ratio between the parent and the fragment ions is provided as a function of photon energy, essential to quantify tBuOOH in gas-phase oxidation/combustion experiments via advanced mass spectrometry techniques.

Diethyl ether (DEE) has been proposed as a biofuel additive for compression-ignition engines, as an ignition improver for homogeneous charge compression ignition (HCCI) engines, and as a suitable component for dual-fuel mixtures in reactivity-controlled compression ignition (RCCI) engines. The combustion in these engines is significantly controlled by low-temperature (LT) chemistry. Fundamental studies of DEE LT oxidation chemistry and of its influence in fuel-mixture oxidation are thus highly important, especially at elevated pressures. Elevated pressure speciation data were measured for the LT oxidation of DEE, of its similarly-structured linear five-heavy-atom hydrocarbon fuel (n-pentane), and of a mixture of the two fuels in a jet-stirred reactor (JSR) in the temperature range of 400–1100 K and at various pressures up to 10 bar. The pressure influence on the LT oxidation chemistry of DEE was investigated by a comparison of the measured profiles of oxidation products. The results for DEE and n-pentane were then inspected with regard to fuel structure influences on the LT oxidation behavior. The new speciation data were used to test recent kinetic models for these fuels [Tran et al., Proc. Combust. Inst. 37 (2019) 511 and Bugler et al., Proc. Combust. Inst. 36 (2017) 441]. The models predict the major features of the LT chemistry of these fuels well and could thus subsequently assist in the data interpretation. Finally, the LT oxidation behavior of an equimolar mixture of the two fuels was explored. The interaction between the two fuels and the effects of the pressure on the fuel mixture oxidation were examined. In addition to reactions within the combined model for the two fuels, about 80 cross-reactions between primary reactive species generated from these two fuel molecules were added to explore their potential influences.

International audience; The oxidation of neopentane was studied in jet-stirred reactors at atmospheric pressure over a temperature range 500–850 K and ϕ = 0.5. The products were analyzed with chromatographic, mass spectrometric, and photoelectron spectroscopic setups complemented with theoretical calculations. This combination provides a comparison of photo-ionization mass spectrometry and gas chromatography for the quantification of mole fractions and highlights the relevant differences between them, while mass-tagged photoelectron spectroscopy sheds light onto the isomeric distribution. The new data and corresponding analyses are expected to provide valuable guidance for an extension of the kinetic model and the choice of experimental methods. The main first and second O2-addition products were observed in agreement with the literature (e.g., 3,3-dimethyloxetane, acetone, isobutene, and γ-ketohydroperoxide). The simulated mole fractions of the products using a literature kinetic model were compared to the experimental results. Even though the kinetic model has been validated previously, significant discrepancies between the measured and simulated mole fractions of 2-methylpropanal and methacrolein, two fuel-specific low-temperature oxidation products, were found. Furthermore, some experimentally observed species related to γ-ketohydroperoxide decomposition were not predicted indicating that the model is incomplete. The detection of 2-methylpropanal and formic acid highlighted the importance of the Korcek-type pathway.

International audience; Lignocellulosic biomass is the most abundant carbon source and it is a base of the whole biorefinery concept. Levoglucosan (1,6-anhydro-β-D-glucopyranose) (LG) is an anhydrous sugar formed as a major product during pyrolysis of cellulose. LG might be a promising chemical platform. It can be converted to different high added-value chemicals such as levoglucosenone, 5-hydroxymethylfurfural and styrene directly or through a glucose intermediate via chemical, catalytic and biochemical processes. In this critical review we focus not only on the pyrolytic methods for the synthesis of levoglucosan, but above all also on the recent scientific progress in the chemical and biochemical transformation of levoglucosan to highly valued compounds. The catalytic performances of the heterogeneous and enzymatic catalytic systems used for different reactions of LG conversion are reviewed. Specific properties of the active sites, roles of additives, and solvents and conditions are discussed in detail. We conclude on recommendations to further improve LG conversion to high added-value products.

International audience; The determination of the abundances of the CHx, C=O and aromatic groups in chondritic Insoluble Organic Matter (IOM) and coals by Infrared (IR) spectroscopy is a challenging issue due to insufficient knowledge on the absorption cross-sections and their sensitivity to the molecular environment. Here, we report a calibration approach based on a 13C synthetic model material whose composition was unambiguously determined by Direct-Pulse/Magic Angle Spinning Nuclear Magnetic Resonance (DP/MAS NMR). Ratios of the cross-sections of the CHx, C=O and aromatic groups have been determined, and the method has been applied to IOM samples extracted from four chondrites as Orgueil (CI), Murchison (CM), Tagish Lake (C2-ungrouped) and EET 92042 (CR), and to a series of coals. The estimate of the aliphatic to aromatic carbon ratio (nCHx/nAro) in IOM samples from Orgueil, Murchison and Tagish Lake chondrites is in good agreement with Single-Pulse/NMR estimates earlier published, and is lower by a factor of 1.3 in the case of the CR chondrite EET 92042 (but the error bars overlap). In contrast, the aliphatic to carbonyl ratio (nCHx/nC=O) is overestimated for the four chondrites. These discrepancies are likely due to the control of the absorption cross-section of the C=O and C=C bonds by the local molecular environment. Regarding coals, the use of published NMR analyses has brought to light that the integrated cross-section ratio ACHx/AAro varies with the vitrinite reflectance over an order of magnitude. Here as well, the local oxygen speciation plays a critical control in AAro, which decreases with increasing the vitrinite reflectance. We provide an analytical law that links ACHx/AAro and vitrinite reflectance, which will allow the determination of nCHx/nAro for any coal sample, provided its vitrinite reflectance is known.

International audience; Di-n-butyl ether (DBE, C8H18O) has been proposed as a promising biofuel for diesel engines, but details of its low-temperature (LT) oxidation chemistry are not well understood. This paper reports new speciation data obtained in the temperature range of 400–1100 K at ϕ=1 and nearly-atmospheric pressure, using a plug flow reactor combined with electron ionization molecular-beam mass spectrometry (MBMS) and two different jet-stirred reactors coupled with either online gas chromatography or tunable synchrotron vacuum ultraviolet photoionization-MBMS.The experimental results confirm that DBE is very reactive and exhibits two negative-temperature coefficient (NTC) zones around 500–550 K and 650–750 K. Speciation data with about 40 C0-C8 species are presented, including about 20 LT species not reported previously. Among those, fuel-specific C8H16O2 cyclic ethers were quantified. Also, butanoic acid, which is present in highest amounts among the detected LT intermediates, and C8H14O3 diones, were found to peak already near 500 K, suggesting their importance in the LT chemistry of DBE. Signals of several highly oxygenated peroxides (e.g., C8H14O5 and C8H16O6) were detected, indicating third O2 addition steps. Respective reaction pathways are suggested and discussed based on these experimental results.To better understand the LT chemistry of DBE, the present data were compared to two recent DBE models (Cai et al., 2014; Thion et al., 2017). Significant discrepancies between the experimental data and both models were found for important LT intermediates, of which many were not included in the respective mechanisms. The results reported in the present study thus provide new opportunities for refining DBE kinetic models.

International audience; Diethyl ether (DEE) has been recently suggested as a potential biofuel for compression-ignition engines that are known to be significantly controlled by low-temperature (LT) chemistry. However, the LT oxidation of DEE has not fully been understood in term of the formation of LT fuel-specific products. We have thus studied the oxidation of DEE by examining detailed profiles of its oxidation products under LT conditions (400-1100 K). To this end, we have used a dedicated experimental setup including a nearly-atmospheric jet-stirred reactor (JSR) coupled to online gas chromatography (GC). The experiments were complemented by measurements made with a JSR coupled to tunable synchrotron vacuum ultraviolet (SVUV) photoionization (PI) molecular-beam mass spectrometry (MBMS) for a cross-validation of the identification of important LT species. Experimental results indicate that DEE is very reactive; it starts to react around 425 K. DEE exhibits an unusual oxidation behavior with two negative temperature coefficient (NTC) zones in the JSR study. Because of this two-NTC observation, additional experiments were performed with a plug flow reactor (PFR) combined with electron ionization (EI)-MBMS, confirming this behavior in the two types of reactor. Moreover, about 20 oxidation species in C1-C4 range were detected with several intermediates containing 2-3 O-atoms. Acetic acid is found to peak at 525 K with a very large amount, suggesting that it is a key species in the early stage of DEE's LT oxidation. Possible DEE-consumption paths leading to acetic acid formation could play an important role in the oxidation mechanism of DEE. A new model is proposed based on the present experimental observations to include new primary LT reaction paths. The model reproduces the experimental phenomena quite well and enhances the understanding of the two-NTC-zone occurrence and of intermediates containing 2-3 O-atoms during the LT oxidation of DEE.

PIARC 2018, The 15th International Winter Road Congress, Gdansk, POLOGNE, 20-/02/2018 - 23/03/2018

Understanding the chemistry behind the oxidation of ammonia/hydrogen mixtures is crucial for ensuring the flexible use of such mixtures in several applications, related to propulsion systems and power generation. In this work, the oxidation of ammonia/hydrogen blends was investigated through an experimental and kinetic-modeling study, where the low- and intermediate-temperature conditions were considered. An experimental campaign was performed in a flow reactor, at stoichiometric conditions and near-atmospheric pressure (126.7 kPa). The mole fraction of fuels, oxidizer and final products was measured. At the same time, a comprehensive kinetic model was set up, following a modular and hierarchical approach, and implementing the recently-available elementary rates. Such a model was used to interpret the experimental results, and to extend the analysis to literature data, covering several oxidation features. The reactivity boost provided by H2 addition was found to be approximately linear with its mole fraction in both flow- and jet-stirred-reactor conditions (except for the smallest H2 amounts in the flow reactor), in contrast with the more-than-linear increase in the laminar flame speed. The key role of HO2 in regulating fuel conversion and autoignition at low temperature was confirmed for binary mixtures, with H2NO being the bottleneck to the low-temperature oxidation of NH3-rich blends. On the other hand, the nitrogen fate was found to be mostly regulated by NHx + NO propagation and termination channels.

openaire: EC/H2020/101006744/EU//EHLCATHOL Small aromatic molecules with oxygen-containing functional groups (monoaromatic oxygenates) are common products of the catalytic depolymerization of lignin, which can be considered as a promising class of fuel additives. This mini-review article starts with an introduction of second generation (2G) of biofuel production from lignocellulose and the further conversion of lignin into fuel performance boosting blends. The discussion is divided into four parts. The first part gives a brief overview of the production of aromatic oxygenates from the catalytic conversion of lignin of different origin. The three following parts are focused on the aromatic oxygenates, for which combustion data can be found. The second part describes their chemical structure and physical properties. The third part is dominated by their global combustion performance, i.e., the commercial fuel parameters as lower heating value, octane and cetane numbers. A few studies on ignition delay times and laminar flame velocities are also described. The fourth part shortly reviews the kinetic studies presenting product quantifications, the proposed detailed kinetic models and the influence of the structure of the aromatic reactant on soot formation. To finish, a perspective on future research directions is given.

We report the design and synthesis of europium-doped gadolinium oxysulfide nanoscintillators Gd2 O2 S:Eu3+ conjugated with two different photosensitizers (PSs): a zinc chlorin (ZnTPC) and a zinc phtalocyanine (ZnPc) by covalent bonding through a layer of N-(3-trimethoxysilylpropyl)diethylenetriamine (TPDA). These conjugates were designed to be activated under X-ray excitation to allow a photodynamic effect, although this desired outcome was not achieved in this study. The monodispersed nanoparticles of ∼70 nm diameter were pegylated to be stabilized in aqueous suspension. It was shown that the PSs conserved their photophysical properties once conjugated to the nanoscintillator and efficient singlet oxygen was obtained upon photo-irradiation. However, no energy transfer was observed from the nanoscintillator to the photosensitizer neither under photo- nor X-ray irradiation.

International audience; The reaction chemistry of furanic fuels, proposed as next-generation bio-derived fuels, has been a target of recent studies. However, quantitative intermediate species profiles at low- to moderate-temperature (LMT) conditions remain scarce. The present paper reports the first systematic full speciation dataset in the temperature range 730–1170 K for three furanic fuels, 2,5-dimethylfuran (DMF), 2-methylfuran (MF), and furan, measured for different equivalence ratios under near-identical LMT conditions in a flow reactor at 1 bar. More than 35 species including reactants, intermediate species, and products were analyzed using electron ionization (EI) molecular-beam mass spectrometry (MBMS). These experimental results provided motivation to extend a previous single joint mechanism for the three furanic fuels, developed for the high-temperature regime in low-pressure premixed flames, to include the LMT oxidation chemistry. A decisive difference of the present mechanism versus all previously reported models is a more complete description of fuel radical reactions for LMT oxidation, obtained from theoretical calculations of thermodynamic properties and rate constants.The experimentally observed differences in fuel conversion behavior and species distribution between the three fuels have been compared to model predictions using the newly extended mechanism. The dependence of fuel conversion on equivalence ratio decreases significantly from DMF to furan, a behavior consistent with the different number of lateral methyl groups in the fuel structure. All three furanic fuels, especially DMF, produce several highly toxic oxygenated species including acrolein, methyl vinyl ketone, furfural, and phenol. These toxic species were found to be products of the primary reactions of these fuels, and these undesirable trends could be explained satisfactorily by the present model, pointing to some caution with regard to the potential emission spectra under LMT conditions.

International audience

Flammable gas/solid hybrid mixture explosions are not well understood because of the interaction of the thermal transfer process, the combustion kinetics mechanisms and the interactions between turbulence and combustion. The main objective on this work is to study the explosion severity and flame burning velocities of carbon black nanoparticles/methane to better understand the influence of added nanopowders in gas explosions. Tests have been performed in a flame propagation tube and in the standard 20 L explosion sphere. The influence of carbon black particles on the explosions severity and in the front flame propagation has been appreciated by comparing the results obtained for pure gas mixtures. It appeared that the carbon black nanoparticles insertion increases around 10% the explosion severity for lean methane mixtures. Therefore, it seems that nanoparticles has an impact on the severity of the explosion even for quiescent systems, contrary to systems involving micro-sized powders that requires a dispersion at high turbulence levels. The increment on the maximum rate of pressure rise is higher for powders with lower elementary particle diameter, which is notably due to the fragmentation phenomena. A flame propagation numerical model associated to a gas/carbon black mixture has been developed to examine the influence of carbon blacks on the flame propagation. The results of the numerical model suggest that the radiative heat contribution promotes the flame acceleration. This result is consistent with the experimental increase on the explosion severity for some hybrid mixtures, Les explosions de mélanges de gaz inflammables/solides combustibles ne sont pas bien comprises en raison de la complexité des transferts thermiques, des mécanismes de cinétiques et des interactions entre la turbulence /combustion. L'objectif principal de ce travail est d'étudier la sévérité des explosions des nanoparticules de carbone noir/méthane afin de comprendre l'influence de l'insertion des nanoparticules sur les explosions de gaz. Des tests ont été effectués sur ces mélanges dans un tube de propagation de la flamme et dans une sphère d'explosion standard de 20 L. L'influence de la turbulence initiale et de la taille de particule élémentaire du noir de carbone a également été étudiée. Il semble que l'insertion de nanoparticules de noir de carbone augmente d'environ 10% la sévérité de l’explosion pour les mélanges pauvres en méthane. Par conséquent, il semble que les nanoparticules ont un impact sur la sévérité de l'explosion même pour les systèmes à basse turbulence, contrairement aux systèmes impliquant des poudres de taille micrométrique qui nécessitent une dispersion à des niveaux élevés de turbulence. L'augmentation de la vitesse maximale de montée en pression est plus élevée pour des poudres avec un petit diamètre de particule, notamment en raison des phénomènes de fragmentation. En outre, un modèle numérique de propagation de front de flamme associé à un mélange gaz/noir de carbone a été développé pour examiner l'influence du noir de carbone sur la propagation de la flamme. Les résultats du modèle numérique suggèrent que la contribution de la chaleur radiative favorise l'accélération de la flamme. Ces résultats sont en accord avec les résultats expérimentaux de sévérité de l'explosion pour certains mélanges hybrides

Two halophytes, Atriplex halimus and Atriplex hortensis , were selected to be tested for phytodesalination of road runoff. A 60 d pot experiment was conducted and germination, survival, growth, and bioaccumulation of NaCl and trace metals by both species were monitored in conditions simulating those encountered in road runoff treatment systems. NaCl concentration was controlled in the hydration solution and ranged from 0 to 2 g/L. Germination and survival of young seedlings were not affected by salinity increase in the tested range. Growth was enhanced by NaCl in the hydration solution for A. halimus whereas water content (WC) was significantly and negatively correlated with NaCl concentration. No significant effect of NaCl concentration in the hydration solution was recorded on either growth or WC for A. hortensis . Both Atriplex species accumulated Na + and other cations. Results for Na/K molar ratio indicated that A. halimus was not affected as much as A. hortensis in its homeostasis and nutritional capacities. These results show that both Atriplex species are able to germinate, grow and accumulate sodium when watered with hydration solutions polluted with NaCl. They are therefore good candidates for phytodesalination of road runoff polluted by deicing salts, and should be tested at the pilot scale.

International audience; The activated sludge process (ASP) is the most commonly used process for wastewater treatment. Improving its performance is necessary from economic and environmental point of views. In this context, dynamic optimization is a powerful tool for assisting engineers in determining optimal operations and designs for ASPs. However, the real optimality of the solution strongly depends on the optimization problem statement, for which unfortunately, there is no standard or commonly accepted formulation. In a hopeful attempt to provide a guideline for future works on the topic, this paper reviews the literature devoted to optimal control and design of ASPs. The main issues to be addressed in order to get reliable solutions are discussed , among which: (1) Managing the inevitable mismatch between the model predictions and the real ASP operation. (2) Dealing with the unpredictable variations in the wastewater characteristics. (3) Accounting for the slowest dynamic processes occurring in ASPs. (4) Appropriately selecting the decision variables and the flowsheet structure in order to simplify the problem formulation from a mathematical perspective. (5) Conveniently choosing the cost functions expressions/correlations. (6) Successfully selecting the mathematical constraints in order to guarantee physically relevant operations.

International audience; The pinch off of heterogeneous ferrofluid drops at a nozzle in air was experimentally investigated with a magnetic field (downward or upward) and without a magnetic field. Compared to homogeneous drops, the self-similarity and universal scaling law were verified through modifying the initial conditions, such as the nozzle diameter, flow rate, and magnitude and direction of the magnetic fields. Two pinch-off points were observed, and the two consecutive pinch-off dynamics were characterized through scaling laws. Here our scaling exponent remains within the scope of (0.70-0.80) for the primary whereas it remains within the scope of (0.60-0.70) for the secondary pinch off, respectively, comparable to the classic range from 2/3 to 1 for homogeneous drops. The gravity-compensating and gravity-superimposing magnetic fields display a negligible effect on the exponent but determine the sequence of double pinch offs. The universal character of the self-similar pinch off is extended to a heterogeneous fluid.

International audience; In this work, a multi-objective dynamic optimization of the operating strategy of a small-size wastewater treatment plant is carried out. In-situ incineration of the excess sludge produced for electricity production is investigated in order to reduce the operating costs. The trade-offs between the treatment quality and the operating costs are characterized. Compared to the literature, emphasis is put on a more rigorous formulation of the problem and an accurate modeling of the underlying phenomena so as to get physically relevant solutions. Thus, from a mathematical perspective, the problem is formulated so that the solution is less sensitive to the - arbitrarily chosen-plant initial conditions. Modeling of physical phenomena e.g. the detrimental effect of the concentration of suspended solids in the mixed liquor, on oxygen transfer rate, has been included in the model. Several constraints are added to the problem so as to maintain the optimal solutions within the limits of validity of the mathematical model. The results provided a clear picture about the trade-offs between the treatment quality and the exploitation costs. Sludge incineration was shown to be of a high energetic profit, but it does not allow the plant to be electrically autonomous.

International audience; Anaerobic reactor is one of gas-liquid-solid three-phase bio-reactors and has attracted high attentions worldwide due to biogas, a renewable energy. As is well-known, hydrodynamic conditions play crucial roles in the performance of the three-phase reactors. But the knowledge about the hydrodynamic conditions around sludge (microbial aggregates) is limited. The hydrodynamic shear force exerted on sludge derives from the liquid flow and rising biogas bubbles nearby. The in situ investigation in a two-dimensional micro anaerobic reactor shows that 56.8-96.6% shear rate exerted on one piece of granular sludge (major axis of 2 mm and minor axis of 1.5 mm) in typical motions stems from the rising bubbles when biogas production rate is greater than 0.1 m(3) kgVSS(-1) d(-1), and the superficial liquid velocity of reactor was fixed at 6.48 mh(-1) in this study. Furthermore it linearly correlates with specific bubble population with R-2 of superior to 0.95. The specific bubble population plays more important roles in the shear rate on granules than the bubble diameter. Liquid flow is also important for the shear rate exerted on moving sludge in term of the relative velocity between sludge and liquid flow rather than the superficial liquid velocity. Thus the shear rate derived from liquid flow would be significantly lower than that part originated from bubbles. A high-speed digital camera and a particle image velocimetry (PIV) system were used to in situ quantify the bubbles and their behavior in reactor. This study could facilitate understanding and improving the hydrodynamic conditions in three-phase bio-reactors.

International audience

The oxidation of dimethylether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K, equivalence ratios of 0.25, 1 and 2, residence time of 2 s, pressure of 106.7 kPa (close to the atmospheric pressure) and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde which is one of the major product from DME oxidation as well as that of hydrogen peroxide which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bar on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine and flame data from literature. The kinetic analysis of the model enabled to highlight some specificities of the oxidation chemistry of DME: 1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H-atom abstraction) with oxygen yielding an olefin + HO2●; 2) the low-temperature reactivity is driven by the relative importance of the second addition to O2 (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting effect. 119

International audience; The purpose of this study was to evaluate the mixing characteristics of a new milliliter-scale (mL-scale) reactor developed for studying enzymatic activity or physiological cell response. The mL-scale reactor was designed to enable the integration of several sensors to carry out dynamic measurements in a controlled environment. Rapid homogeneity of the entire system is essential to ensure reproducible and reliable results, consequently the reactor was stirred to optimize both mass and heat transfers. A comparative study using three different techniques was undertaken to study mixing performances in the system. Firstly, mixing time (4,) was estimated in the reactor using both experimental methods, including instrumental method and image analysis, and CFD. As hydrodynamics is not occurring in the fully-turbulent regime, turbulent numerical simulations using the SST transitional and the standard k-epsilon turbulence models were conducted and compared to laminar approach. Results showed good agreement between the two experimental methods and no significant differences were observed between the simulation methods. Moreover, according to results, a minimum agitation rate of 350 rpm seemed to be appropriated to obtain a quick homogenization in the system. Finally, the second part of the study seemed to indicate that probes had no significant impact in the studied reactor.

International audience; The purpose of this work is to analyze the efficiency of natural adsorbents (rice husk ash (RHA) versus corn husk ash (CHA)) for the dry purification of ethyl biodiesels obtained by transesterification via homogeneous catalysis of nonedible oils (Balagnites aegyptiaca, Azadirachta indica, and Jatropha curcas). The characterization of RHA and CHA was achieved by N2 adsorption/Brunauer–Emmett–Teller analysis and by scanning electron spectroscopy with microanalysis by energy dispersive X-ray spectroscopy. The quality of the three biodiesels, before and after dry treatment on adsorbent, was evaluated by various analytical methods (1H nuclear magnetic resonance, gas chromatography with a flame ionization detector, Karl Fischer titration, and inductively coupled plasma–atomic emission spectroscopy). Several operating conditions (presence of activated carbon in the ashes, temperature, contact time, and number of treatment cycles) were tested in order to define the best procedure. RHA combined with the selected procedure showed very satisfactory results for removal of impurities from the produced biodiesels (residual glycerides, free glycerin, water, catalyst, and metals introduced during the oil extraction) and thus may be an alternative to the conventional wet purification process (acidic water washing).

International audience; This work aims at investigating the breakup dynamics of the ferrofluid droplet under magnetic fields in a microfluidic T-junction. The whole breakup processes of the ferrofluid droplets under uniform magnetic field and non-uniform magnetic field were exhaustively considered. The influence of both the flow rates and magnetic flux density on the formation and breakup were extensively studied. It was found that the type of breakup process can be changed and the breakup frequency of ferrofluid droplets can be actively modulated by applying a uniform magnetic field. While under non-uniform magnetic field, the asymmetric breakup of ferrofluid droplets can be realized. Both the magnetic field intensity and hydrodynamic force affect the asymmetry of the breakup process. The non-uniform magnetic field can exert attraction on ferrofluid droplets in a dissymmetrical way to avoid breakup.

International audience; Ammonia has a potential as carbon-free and high-energy density compound for chemical storage of renewable energies and its synthesis from green H2 requires to be as energetically efficient as possible. In this work, a superstructure optimization methodology for process synthesis is proposed and applied to an ammonia production process. The approach covers three different scales: process, equipment, and molecules. Process scale refers to finding the optimal process structure, while the equipment scale is related to the best set of operating conditions, and the molecular scale studies two catalysts (Fe and Ru) with their respective kinetic rates. The optimization intends to minimize the Levelized Cost of Ammonia (LCOA) and maximize the energy efficiency. The best trade-off is found with the Ru catalyst, with an LCOA of 766 €/tNH3 and 57.2 % of energy efficiency. In comparison with reference cases, the LCOA decreases 0.6 % and the energy efficiency increases 1.5%. The main improvement is found in the pressure, 75 bar, reduced in 25 %. The production of 11.6 tNH3/day equals to 2.5 MW of stored power from 3 MW supplied as H2 to the process, with a total energy consumption of 10.67 kW h/kgNH3, including prior H2 and N2 production processes.

Effective capture of polar volatile organic compounds under environmental conditions is a challenge owing to the adsorption competition between polar volatile organic compounds and water.

International audience; Thermal oxidation stability of liquid jet fuels remains a significant scientific challenge in the development of modern aviation. This study aims at experimentally and numerically investigating the autoxidation of n-decane, which is used as a component of jet fuel surrogates in the literature. Induction periods (IP) of n-decane were measured in a PetroOxy device under 7 bar of oxygen and cell temperatures varying from 403 to 418 K. IPs give a quantitative measure of the oxidation stability of a fuel. In addition to IPs measurements, the total hydroperoxides content at the end of the IP test was quantified using two iodometric titration methods: colorimetry and potentiometry. In order to simulate the oxidation of the homogeneous liquid phase as a batch reactor, we developed a physical model based on the so-called gamma-phi thermodynamic approach to calculate the compositions of liquid- and gas-phases at the set temperatures and pressures. Based on a state-of-the-art method to capture solvent effects, a detailed kinetic model for the n-decane autoxidation was developed. The simulations are consistent with experimental data from this study (IP and hydroperoxides concentration profiles) and from the literature. The proposed model is validated to simulate the thermal oxidation stability of liquid n-decane, for conversions up to 15 %. Kinetic analyzes highlight the central role played by hydroperoxides decomposition and the self-termination of peroxy decyl (ROO·) radicals in the autoxidation of n-decane.

The large application potential of microbiomes has led to a great need for mixed culture methods. However, microbial interactions can compromise the maintenance of biodiversity during cultivation in a reactor. In particular, competition among species can lead to a strong disequilibrium in favor of the fittest microorganism. In this study, an invert emulsion system was designed by dispersing culture medium in a mixture of sunflower oil and the surfactant PGPR. Confocal laser scanning microscopy revealed that this system allowed to segregate microorganisms in independent droplets. Granulomorphometric analysis showed that the invert emulsion remains stable during at least 24 h, and that the introduction of bacteria did not have a significant impact on the structure of the invert emulsion. A two-strain antagonistic model demonstrated that this invert emulsion system allows the propagation of two strains without the exclusion of the less-fit bacterium. The monitoring of single-strain cultures of bacteria representative of a cheese microbiota revealed that all but Brevibacterium linens were able to grow. A consortium consisting of Lactococcus lactis subsp. lactis biovar diacetylactis, Streptococcus thermophilus, Leuconostoc mesenteroides, Staphylococcus xylosus, Lactiplantibacillus plantarum and Carnobacterium maltaromaticum was successfully cultivated without detectable biotic interactions. Metabarcoding analysis revealed that the system allowed a better maintenance of alpha diversity and produced a propagated bacterial consortium characterized by a structure closer to the initial state compared to non-emulsified medium. This culture system could be an important tool in the field of microbial community engineering.

International audience; The prediction of solvation quantities is an important issue in several fields of chemical and process engineering. In this regard, this work was conducted to increase the prediction power of the equation-of-state (EoS) approach by coupling the tc-PR (translated-consistent Peng-Robinson) EoS with COSMO-RS (Conductor-like Screening Model for Real Solvents) as gE model through an advanced mixing rule. Since the only input parameter of the COSMO-RS model is the charge density (σ) profile of each molecule, the resulting EoS (called tc-PR/COSMO-RS) does not require any binary interaction parameter contrary to other predictive cubic EoS, such as VTPR, PPR78, PSRK, and UMR-PRU. This feature allows the quantification of solvation data of a great number of systems from readily available pure-component properties (critical temperature and pressure, acentric factor and σ -profile). Satisfactory results were obtained for the prediction of solvation Gibbs energy data that were extracted from the extensive CompSol database (the average absolute deviation is 0.30 kcal/mol). The proposed model represents a very flexible alternative for the prediction of solvation data, since it can deal with a large variety of solutes in either a pure or mixed solvent, and for the entire phase diagram (including the supercritical region).

International audience

Nowadays, superhydrophobicity has been the limelight of the academic community owing to the plethora of applications. In this work, the downhill motion of liquid drops and liquid marbles was investigated by two distinct particle-laden interfaces. Liquid drops and liquid marbles accelerate firstly and then move on the slope with a steady velocity which decreases with the liquid viscosity. The steady velocity of liquid marbles is lower than that of liquid drops while the maximum aspect ratio of liquid marbles is higher than that of liquid drops, due to different interface interactions. The particles on the solid substrate enhance the motion of liquid drops while those on the liquid surface reduce the surface tension of liquid marbles. Both liquid drops on non-stick solid surface and non-stick liquid marbles on solid substrate could provide theoretical basis for the precisely targeted transportation of small quantities of liquids by particle-laden interfaces, especially in chemical and biomedical applications.

International audience; Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn 2+-doped Ag−In−Ga−Zn−S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag + , In 3+ , Ga 3+ , and Zn 2+ and of Mn(stearate) 2 in oleylamine. The influence of the Mn 2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn 2+), and robust photo-and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM −1 s −1 and r 2 = 0.57 mM −1 s −1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.

International audience; Despite decades of research on alkene ozonolysis, the kinetic network of the archetypal case of ethylene (CH2[double bond, length as m-dash]CH2) with ozone (O3) still lacks consensus. In this work, experimental evidence of an elusive diradical pathway is provided through the detection of the 2-hydroperoxyacetaldehyde ketohydroperoxide and its decomposition product, glyoxal.

International audience; Folate receptor α (FRα) is overexpressed on numerous tumorous cell types such as ovarian or endometrial cancer cells. Moreover, FRα is absent from most healthy tissues as it is normally expressed only on the surface of proximal tubules cells of kidneys and choroid plexus. Thus, folate-based radiopharmaceuticals have emerged this last two decades as FRα is a target of choice to diagnose and treat numerous cancers. Nuclear imaging is a performing diagnostic technology using highly sensitive detectors and specific radiopharmaceuticals used to detect tumors at an earlier stage. Herein, an overview of the development of folate-based radiopharmaceuticals to detect FRα-positive tumors by nuclear imaging using positron emission tomography (PET) and single photon emission computed tomography (SPECT) is exposed. Strategies developed to improve precursor synthesis, bioavailability, clearance, and affinity to FRα will be detailed. Advances made to decrease kidney uptake open the gate to targeted radionuclide therapy (TRT) using folate-based radiopharmaceuticals to treat FRα-positive tumors. Thus, radiofolates used in TRT and more precisely in a theranostic approach will be depicted in this review

International audience; Abstract An NMR/MRI methodology is developed for the study of flows in miniaturized systems handling volumes of fluid in the microliter range. Specific MRI devices are implemented, including radiofrequency coils with millimetric dimensions whose size and geometry correspond to the studied systems. We follow a low-cost development procedure of home-made milli-RF coils, including their dimensioning, the simulation of the produced electromagnetic field, their fabrication and their integration in experimental devices. In each of the two cases presented the filling factor is optimized and the sensitivity of the measurement is greatly improved over standard commercial instrumentations by a factor up to 17. Two applications are then discussed: the characterization of the hydrodynamics in an anchor shaped micromixer and the monitoring of the development of a biofilm at the pore scale.

Food transition requires the replacement in human diet of animal-based proteins by alternative sources of proteins including plant-based proteins. This calls for a detailed knowledge of the functional properties of plant-based proteins, including their surface activity. In this framework, we provide here a comparative study of the interfacial properties of two plant proteins, extracted respectively from wheat and sunflower. We combine time- and concentration-dependent measurements of the surface tension and the surface rheology, as measured with a pendant-drop set-up, and of the surface excess concentration, as measured by ellipsometry, of plant protein interfacial films. We demonstrate a time-concentration superposition principle for the surface pressure and surface excess concentration, showing that the kinetics for the building of the interfacial films is essentially governed by the diffusion of the proteins from the bulk to the interface. We find that the rheological and structural properties of the interfacial protein films show markedly different behaviors for the two classes of protein, which is encoded in the structural features of the individual proteins: wheat proteins are more surface active than sunflower proteins, are keen to compress and re-arrange at an air-water interface, whereas sunflower proteins do not. This work provides qualitative and quantitative analysis of the comparative interfacial behavior of flexible and rigid plant proteins extracted respectively from wheat and sunflower, and demonstrates that a combination of several experimental techniques is necessary to obtain insightful information on the interfacial properties of any species.

International audience

International audience; The accurate and high-throughput generation of kinetic data for combustion detailed chemical kinetic models remains a challenge given the large size of these models. For large organic molecules, the majority of kinetic data of the kinetic models are estimated using quantitative structure activity relationships within reaction classes and reaction rate rules approaches. In this work, we question the limits of the rate rule approach for the isomerization reaction classes, using electronic structure calculations and reaction rate theories. Systematic calculations were performed to investigate the effect of the size and the degree of branching of alkyl radicals on the rate coefficients and their consequences on the rate rule approach. Our computed kinetic data show that when the size of alkyl group is increased, the rate coefficients remains close to each other. This allows the use of methyl as representative models of larger alkyl groups to investigate the influence of increasing the degree of branching. The computed rate coefficients for 1,3-and 1,4-H-atom shifts show that the increase of the branching level, with spectator methyl groups in the transition state cyclic structure can strongly increase the rate coefficients, up to several orders of magnitude. Consequently, a single rate rule is not feasible for any degree of branching of a reaction belonging to the same isomerization reaction class. As variation in rate coefficients are important, this would lead to an explosion of the number rate rules as a function of branching in 5-, 6-, and 7membered cyclic transition states. A new approach is demonstrated and proposed where model transition states are tabulated, and methyl groups are assumed as alkyl groups and all combinations of substitutions in the model TSs, for a given reaction class, are included in a table with associated ab initio rate coefficients. The automation of the construction of such tables is possible and could be an interesting high-throughput / high-accuracy alternative to on-the-fly ab initio calculations of kinetic parameters.

Process intensification has emerged as a strategy to satisfy the objectives of process efficiency, sustainable development and economic competitiveness. Unfortunately, intensified technologies are too numerous to fit in a time-constrained academic syllabus. For high pedagogic impact, appropriate case studies should be favored to cover a wide range of strategies while demonstrating these opportunities, using accessible tools and concepts. The developed case study demonstrates the gain of sustainability offered by applying multi-scale design to a cyclonic separation, enabling miniaturization at constant efficiency. The analysis leads to well-known multi-cyclonic systems. This example is particularly striking for students since multi-cyclonic vacuum cleaners are a domestic illustration of this strategy. The analysis aims to miniaturize the separator, at constant efficiency and dissipated mechanical power. By applying a scale factor to cyclone dimensions, while maintaining the efficiency, a first strategy demonstrates that miniaturization alone cannot be sustainable. The best strategy considers parallel miniature cyclones, which enables to satisfy all objectives: the volume and dissipated mechanical power can be reduced simultaneously, requiring a multi-objective optimization. Scenarios for integration of the case study in various curricula are proposed, by differentiating the learning outcomes as a function of student level and course objectives.

International audience; The electrochemical regeneration of the NADH cofactor was realized in a hybrid flow reactor coupling fuel cell technology and redox flow device, paying attention to the robust immobilization of all catalysts. The rhodium catalyst Rh(Cp∗)(bpy)Cl+ was covalently immobilized on a MWCNT layer and the association with the gas diffusion electrode was carefully optimized. High stability and activity of the electrochemical system were assessed by cyclic voltammetry and amperometry in the flow reactor. Afterwards, the optimal cofactor regeneration was applied to NADH-dependent biosynthesis using immobilized lactate dehydrogenase for the conversion of pyruvate to lactate in the flow cell in the presence of cofactor concentration as low as 10 μM. 79 % faradaic efficiency was achieved and remarkable total turnover number (TTN) were reached: 2500, 18000, and 180000, for the NADH cofactor, the Rh complex and the LDH enzyme, respectively.

International audience; Given the increasing demand for nickel (Ni) in the Li-ion battery industry, the agromining chain of processes, based on phytomining of Ni combined with hydrometallurgy, has the potential to form an important source of Ni. Currently, plants grown on Ni-rich soils (in this case Odontarrhena chalcidica), having hyperaccumulated Ni, are ashed, and the Ni is transferred from ash to solution by sulfuric acid leaching. This work focuses on the recovery of Ni-sulfate from this strongly acidic leachate that contains many cations. For this purpose, a bispicolylamine-based chelating resin (Dowex M4195) was tested to better understand the functioning of this resin under these conditions. Column experiments were performed with model synthetic solutions containing Ni and Na-sulfate at pH 2. A set of reactions has been formulated to describe the interactions involved and used in a model combining transport in porous media and chemical reactions at equilibrium. Excellent agreement between the experimental and the calculated breakthrough curves were obtained by adjusting only two parameters. The set of reactions and parameters allowed to fit with sufficient accuracy the breakthrough curves obtained from an ash leachate of the hyperaccumulator plant O. chalcidica. A better understanding of the use of the Dowex M4195 resin for the extraction of Ni from a strong acid multicomponent solution has been achieved, and this separation has been shown to be promising for the recovery of Ni extracted from hyperaccumulator plant bio-ores as part of the agromining process.

International audience; The computation of solvation energies has many uses in several fields, such as design of separation processes, pharmacology and drug-design, and kinetic modeling. These applications require thermodynamic models capable of accurately predicting solvation energies, accounting for the temperature dependency of this property, and which are fast and robust. Within this framework, we compared two COSMO-based continuum solvation models (COSMO-RS and COSMO-SAC-dsp) with two versions of predictive cubic equations of state well-acknowledged for their efficiency (PSRK and UMR-PRU). For this purpose, a large experimental set of 65,000 datapoints extracted from the COMPSOL databank was considered. Comparisons between computed and experimental data were performed for Gibbs solvation energy and, for the first time in the literature, for both entropy and enthalpy of solvation simultaneously. For simpler binary mixtures, in which hydrogen bonding does not take place, all models were capable of providing accurate predictions, with average absolute deviations below 0.3 kcal/mol regarding the solvation Gibbs energy. For more complex associating mixtures, COSMO-RS showed the best correlation between experimental and calculated data, especially for aqueous systems; among EoS, it is observed that the PSRK model offers the best accuracy.

National audience; Les observations effectuées par les instruments embarqués à bord de l’orbiteur Cassini montrent que la croissance moléculaire mise en évidence dans l’ionosphère de Titan mène à la formation d’aérosols. Des études récentes de la physico-chimie de cette couche de l’atmosphère ont établi que les ions lourds positifs et négatifs détectés par spectrométrie de masse sont des embryons d’aérosols.En dépit de ces avancées, de nombreuses interrogations demeurent. Un des objectifs des travaux menés consiste à comprendre le rôle exact des ions dans la formation des aérosols en examinant les collisions élémentaires à l’aide d’un réacteur produisant un écoulement supersonique uniforme couplé à une source sélective d’ions (CRESU-SIS). De façon complémentaire, un autre objectif consiste à simuler la croissance des ions dans un réacteur plasma (PAMPRE) ou photochimique (APSIS) et à comparer les produits ionisés avec les spectres mesurés par les instruments INMS et CAPS-ELS embarqués à bord de Cassini.Pour mener à bien ces études, nous associons modélisateurs, physico-chimistes expérimentateurs et théoriciens. Il est clair en effet que la compréhension de la photochimie des atmosphères planétaires froides, en particulier celle de Titan, passe par l’identification des processus clés ainsi que par l'obtention théorique et expérimentale d'un grand nombre de données fiables et sur les réactions et processus physico-chimiques à très basses températures (< 200 K) et leur utilisation dans des modèles photochimiques atmosphériques réalistes.

High solid anaerobic digestion (HSAD) is a promising technology for the treatment of organic waste. Mixing process in HSAD is quite difficult with long mixing time, poor homogenization, significant short-circuiting and stagnant zones. However, the mass transfer in mixing process in HSAD has not been visualized due to the lack of a proper method. In this study, a novel approach for experimentally quantifying the mass transfer in HSAD’s mixing process was proposed in a mixing tank equipped with multistage impellers by means of the Laser Induced Fluorescence (LIF) technique. Flow field was investigated for better illustrating the mass transfer, thus Particle Image Velocimetry (PIV) and Computational Fluid Dynamics (CFD) technique were conducted for flow field measurement. The obtained results revealed that the feedstock tended to accumulate around the impeller in the HSAD system, especially near the 1st stage. The tracer diffused rapidly around the 1st impeller in t = 10 s, but the diffusion around the 2nd impeller was quite tough even after 4 h 08 min 23 s. And prolonging mixing time could not significantly improve the flow pattern along with the mixing. In this study, new insight was thrown into the visualization of the mass transfer in mixing process within a HSAD reactor. The visualization of mass transfer in the mixing process in HSAD could offer reference information to the study of the mixing process of HSAD even in full-scale.

From 1982–2012, an important legislation, known as Seveso Directives I-II-III and amendments, was adopted in the European Union to regulate and prevent major industrial accident hazards. This European legislation was transposed, applied and implemented in each European Member State and after nearly forty years it is worthwhile to look back and also to look forward to key issues relevant to actual Seveso implementation. Authors of this paper are all members (retired or active) of the Loss Prevention Working Party of the European Federation of Chemical Engineering, which started in 1971. This article examines and compares, for the four EU Member States France, Germany, Italy and Spain, the structures and practices for the implementing of the European rules. Difficulties, variations in application and the quality of enforcement of this complex process are critically discussed, including proper analysis of worked examples. Finally, a particular attention is paid to the different ways in which the control and inspection practices of each of the Member States concerned are implemented.

In the present work, L-glutamic acid production by Corynebacterium glutamicum fermentation on date juice extracts applying two fed-batch feeding modes, pulsed and continuous, were investigated. According to the obtained results, the continuous feeding fed-batch mode was found to be the most efficient process. Moreover the continuous feeding rate mode with a feeding medium containing date juice sugars enriched with ammonium sulfate was found even more favorable as it enhances the L-glutamic acid production by approximately 2.35 fold more than the batch culture and by about 1.17 fold more than the pulsed feeding. In this respect, comparing the traditional batch culture to the continuously fed culture with a medium containing date juice sugars with ammonium sulfate showed increases of 135.47% in L-glutamic acid production, 104% in productivity, 39.09% in biomass, and 47.69% in the yield respectively allowing us to reach a final L-glutamic acid concentration of about 138 g/L, the highest ever published.

International audience; The adsorption of a sunflower protein extract at two air− water and oil−water interfaces is investigated using tensiometry, dilational viscoelasticity, and ellipsometry. For both interfaces, a three step mechanism was evidenced thanks to master curve representations of the data taken at different aging times and protein concentrations. At short times, a diffusion limited adsorption of proteins at interfaces is demonstrated. First, a two-dimensional protein film is formed with a partition of the polypeptide chains in the two phases that depends strongly on the nature of the hydrophobic phase: most of the film is in the aqueous phase at the air−water interface, while it is mostly in the organic phase at the oil−water interface. Then a three-dimensional saturated monolayer of proteins is formed. At short times, adsorption mechanisms are analogous to those found with typical globular proteins, while strong divergences are observed at longer adsorption times. Following the saturation step, a thick layer expands in the aqueous phase and appears associated with the release of large objects in the bulk. The kinetic evolution of this second layer is compatible with a diffusion limited adsorption of the minor population of polymeric complexes with hydrodynamic radius R H ∼ 80 nm, evidenced in equilibrium with hexameric globulins (R H ∼ 6 nm) in solution. These complexes could result from the presence of residual polyphenols in the extract and raise the question of the role of these compounds in the interfacial properties of plant protein extracts.

The unique geometry of screw extruders allows handling very viscous media; thus, they can be used as continuous reactors to conduct polymerization reactions without using any solvents. This is call...