Electrical properties of V2O5–WO3/TiO2 EUROCAT catalysts evidence for redox process in selective catalytic reduction (SCR) deNOx reaction

Electrical conductivity measurements on EUROCAT V₂O₅–WO₃/TiO₂ catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH₃ to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH₃ without O₂, and (ii) 2000 ppm NO + 2000 ppm NH₃ + 500 ppm O₂) to put in evidence redox processes in SCR deNO_x reaction.It was first demonstrated that titania support contains certain amounts of dissolved W⁶⁺ and V⁵⁺ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO₃/TiO₂ precursor of V₂O₅–WO₃/TiO₂ EUROCAT catalyst. It contained an average amount of 0.37 at.% W⁶⁺dissolved in titania, i.e. 1.07 × 10²⁰ W⁶⁺ cations dissolved/cm³ of titania. For the fresh catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved in titania were found to be equal to 1.07 × 10²⁰ and 4.47 × 10²⁰ cm⁻³, respectively. For the used catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved were found to be equal to 1.07 × 10²⁰ and 7.42 × 10²⁰ cm⁻³, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 10²⁰ additional V⁵⁺ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO⁻ and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH₃ reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. N^o atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to

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. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

Parallelised production of fine and calibrated emulsions by coupling flow-focusing technique and partial wetting phenomenon

The capacity of microfluidic technology to fabricate monodisperse emulsion droplets is well established. Parallelisation of droplet production is a prerequisite for using such an approach for making high-quality materials for either fundamental or industrial applications where product quantity matters. Here, we investigate the emulsification efficiency of parallelised drop generators based on a flow-focusing geometry when incorporating the role of partial wetting in order to make emulsion droplets with a diameter below 10 μm. Confinement intrinsically encountered in microsystems intensifies the role played by interfaces between liquids and solids. We thus take advantage of partial wetting to enhance the maximum confinement accessible due to liquid flow focusing. We compare the performances brought by partial wetting to more established routes such as step emulsification. We show that the step configuration and the partial wetting regime are both well suited for being parallelised and thus open the way to the production of fine and calibrated emulsions for further applications. Finally, this new route of emulsification that exploits partial wetting between the fluids and the channel walls opens possibilities to the formation of substantially smaller droplets, as required in many fields of application.     

Study of the telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol. Application to the synthesis of a new macromonomer

The telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol initiated by 2,2′-azobisisobutyronitrile was first investigated at 70 °C and the influence of the type of solvent was studied. The results showed that well-defined telomers of DMAEMA could not be synthetized via telomerization of DMAEMA in water or water/acetonitrile mixture since the telomerization reaction is in competition with the nucleophilic addition of thiol onto the monomer. Transfer constants for mercaptoethanol in benzene and acetonitrile were determined by Mayo's and O'Brien's methods. The transfer constant obtained in acetonitrile (0,6) was higher than that obtained in benzene. This difference can be explained by the fact that the thiol was consumed by two reactions: nucleophilic addition and telomerization. The influence of solvents on the polymerization kinetics was enlightened. These results were applied to the synthesis of macromonomers of DMAEMA with isocyanatoethyl methacrylate (IEM). These macromonomers were copolymerized with styrene.     

Characterization of cationic water-soluble polyacrylamides

Copolymers of poly(acrylamide-co-acryloyloxyethyltrimethylammonium chloride or AM–CMA) and poly(acrylamide-co-methacryloyloxyethyltrimethylammonium chloride or AM–CMA) prepared by inverse emulsion polymerization were characterized by different analytical techniques. The chemical composition of the copolymers was estimated by elemental analysis and by nuclear magnetic resonance spectroscopy (NMR). NMR spectroscopy and computer simulation were further used for investigating the polymers' sequence distribution. The poly(AM–CMA) copolymers are chemically more homogeneous than are the poly(AM–CMA). The configurational propagation of dyads and triads for the homopolymers obeys Bernouilli's statistics. For the copolymers, the chemical sequences distribution is governed by Markov's first-order statistics.     

冠带层新平台技术

子午线轮胎出现不久，就采用钢丝带束层代替了纤维带束层，这对于实现子午线轮胎提高使用寿命和改善操纵性能的潜能是必要的。     

Dynamic mechanical properties and morphology of high‐density polyethylene/CaCO3 blends with and without an impact modifier

Dynamic mechanical analysis and differential scanning calorimetry were used to investigate the relaxations and crystallization of high‐density polyethylene (HDPE) reinforced with calcium carbonate (CaCO₃) particles and an elastomer. Five series of blends were designed and manufactured, including one series of binary blends composed of HDPE and amino acid treated CaCO₃ and four series of ternary blends composed of HDPE, treated or untreated CaCO₃, and a polyolefin elastomer [poly(ethylene‐co‐octene) (POE)] grafted with maleic anhydride. The analysis of the tan δ diagrams indicated that the ternary blends exhibited phase separation. The modulus increased significantly with the CaCO₃ content, and the glass‐transition temperature of POE was the leading parameter that controlled the mechanical properties of the ternary blends. The dynamic mechanical properties and crystallization of the blends were controlled by the synergistic effect of CaCO₃ and maleic anhydride grafted POE, which was favored by the core–shell structure of the inclusions. The treatment of the CaCO₃ filler had little influence on the mechanical properties and morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3907–3914, 2007     

Distributed control of nonlinear diffusion systems by input–output linearization

This paper addresses the distributed control by input–output linearization of a nonlinear diffusion equation that describes a particular but important class of distributed parameter systems. Both manipulated and controlled variables are assumed to be distributed in space. The control law is designed using the concept of characteristic index from geometric control by using directly the PDE model without any approximation or reduction. The main idea consists in the control design in assuming an equivalent linear diffusion equation obtained by use of the Cole–Hopf transformation. This framework helps to demonstrate the closed‐loop stability using some concepts from the powerful semigroup theory. The performance of the proposed controller is successfully tested, through simulation, by considering a nonlinear heat conduction problem concerning the control of the temperature of a steel plate modeled by a nonlinear heat equation with Dirichlet boundary conditions. Copyright © 2012 John Wiley & Sons, Ltd.     

Influence of chitosan characteristics on coagulation and flocculation of organic suspensions

Several samples of chitosan with different degrees of deacetylation and of different molecular weights were tested for the coagulation–flocculation of organic suspensions. Organic suspensions were prepared by mixing mushroom powder with tap water. Experiments were carried out at pH 5, pH 7, and pH 9. Because decreasing the pH reduced the amount of chitosan required to reach the required turbidity, at pH 9, a high concentration of chitosan was required to achieve the required treatment levels, whereas the difference was less significant between pH 7 and pH 5 (the required concentration of chitosan was halved). Though viscosity, correlated to the molecular weight of chitosan, affected treatment performance, its influence on the efficiency of coagulation–flocculation could be substantially reduced by slightly increasing the concentration of the polymer. This is of importance in the processing of industrial effluents: the aging of a chitosan solution, which may cause partial depolymerization, and loss of viscosity, will have a limited impact on process efficiency. The degree of deacetylation also has a limited effect on treatment performance, especially when the degree of deacetylation exceeds 90%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2070–2079, 2005     

Cure kinetics of an epoxy/liquid aromatic diamine modified with poly(ether imide)

The cure kinetics and mechanisms of an epoxy oligomer based on diglycidyl ether of bisphenol A (DGEBA), polymerized with a liquid aromatic diamine based on diethyl toluene diamine (DETDA 80), and its blends with poly(ether imide) (PEI) at concentrations of 0–15 wt % were studied with differential scanning calorimetry under dynamic and isothermal conditions. The kinetic analyses were performed with a phenomenological approach. The reaction mechanism of the blends remained the same as that of the neat epoxy. However, the addition of PEI had a marked effect on the cure kinetics in the DGEBA/DETDA 80 system. The rate of reaction decreased with an increase in the thermoplastic content. Diffusion control was incorporated to describe the cure behavior of the blends in the latter stages. Greater diffusion control was observed as the PEI concentration increased and the cure temperature decreased. Polymer blends based on this epoxy/liquid aromatic diamine had not been previously studied from a kinetic viewpoint. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 660–672, 2005