Relationship Between Structure and Glass Transition Temperature in Low-silica Calcium Aluminosilicate Glasses: the Origin of the Anomaly at Low Silica Content

The anomalous behavior of the glass transition temperature ( T _g) in low silica calcium aluminosilicate glasses has been related to the structural modifications observed by neutron and X-ray diffraction. The diffraction data indicate that Al and Si are in tetrahedral sites and that Ca atoms are in distorted octahedral sites. By subtracting the correlation functions for glasses at constant SiO₂ or constant Al₂O₃ content, we have shown that Si and Al atoms are introduced in a different way within the glass structure. Si is present in various Q ⁿ sites, while Al resides in Q³ and Q⁴ sites for glasses with high CaO content and enters fully polymerized Q⁴ sites with increasing SiO₂ or Al₂O₃ content. The higher proportion of Al in Q³ positions at high CaO content yields a depolymerization of the network. The lower connectivity will contribute to a decrease of the viscosity, which may be at the origin of the decrease of T _g for glasses at low silica content.     

Autogenous shrinkage of concrete: a balance between autogenous swelling and self-desiccation

According to physical analyses, the driving force of autogenous shrinkage of concrete is the change in the capillary pressure induced by self-desiccation in its cement matrix. Self-desiccation is caused by the balance between the absolute volume reduction (chemical shrinkage) and the building up of the capillary network. The aim of this study was to quantify the influence of the cement characteristics on the chain of mechanisms leading from hydration to autogenous deformations. Four parameters were selected: (i) for clinker, the amount of C₃A and free lime and the SO₃/K₂O ratio; (ii) for cement, the fineness. To master the experimental area, 16 cements were prepared at the laboratory from pure raw materials. An important number of characterizing techniques were used in the experimental study. Their choice was based on the important parameters drawn from the physical analysis: setting time, suspension-solid transition, hydration kinetics through isothermal calorimetry and nonevaporable water, chemical shrinkage, evolution of relative humidity, capillary porosity and autogenous shrinkage. Using different techniques allowed to determine the precise mechanism of action of each parameter. Results showed that these mechanisms are generally different, even if their macroscopic consequences may be identical. This point will probably be useful for modeling and determining the industrial keys reducing the autogenous shrinkage. The physical mechanisms involved in autogenous deformations were further understood. In particular, this study shows that initial autogenous shrinkage should be considered as a balance between the self-desiccation and an initial swelling phase. The influence of the four parameters considered on this last phenomenon were also characterized.     

Methane calibration burner and C‐factor determination with cone calorimeter – validation of the standardized calibration protocol

The cone calorimeter is one of the major fire tests. In its reference standard ISO 5660‐1, the apparatus (and especially a characteristic of its orifice plate mass flow meter, called C‐Factor) is calibrated using a methane burner set at 5 kW. However, measurements performed in end‐use are in the range 1–10 kW. In addition, standard proposes to check linearity at 1 and 3 kW, which means in the lowest part of the range. This communication establishes the validation of the linearity on the whole range and determines the optimal condition for C‐factor determination. It justifies the technical choices of the standard. Copyright © 2014 John Wiley & Sons, Ltd.     

Experimental study and numerical modeling of mixing by air injection in yield stress fluids using the OpenFOAM software

Mixing by gas injection is an operation used in industrial processes such as wastewater treatment, metallurgy, or methanization in which pressurized gas is injected into a fluid in order to reduce concentrations and temperatures gradients. This study demonstrates how the CFD toolbox OpenFOAM can be used to simulate such flows. Experimental measurements and observations have been performed on a pilot-scale reactor where pressurized air is injected in a yield stress fluid. The volume of fluid method and an adaptive mesh with refinement at the interface have been used to track the gas inclusions. The numerical model accuracy has been assessed by comparing experimental and numerical results related to the bubble's frequency, dimensions, and rising velocities as well as the fluid recirculation, yielded, and unyielded regions in the tank. The influence of injection parameters such as the injection flow rate and the fluid rheological parameters has been quantified.     

Palladium‐Catalyzed [2+1] Cycloadditions Affording Vinylidenecyclopropanes as Precursors of 7‐Membered Carbocycles

Palladium(II) acetate in association with secondary phosphine oxides provides an efficient catalytic system for [2+1] cycloadditions starting from oxanorbornene derivatives and tertiary propargyl esters giving rise to vinylidenecyclopropanes. This reaction is specific to bidentate phosphinito–phosphinous acid ligands generated from secondary phosphine oxides. The [2+1] cycloaddition was found broad in scope with a high tolerance to various functional groups. Moreover, vinylidenecyclopropanes were straightforwardly converted into oxabicyclo[3.2.1]oct‐2‐ene derivatives through a palladium‐catalyzed ring‐expansion. Finally, the oxa bridge cleavage of oxatricyclic compounds yields functionalized 7‐membered carbocycles.

     

Irreversible changes in protein conformation due to interaction with superparamagnetic iron oxide nanoparticles

The understanding of the interactions between nanomaterials and proteins is of extreme importance in medicine. In a biological fluid, proteins can adsorb and associate with nanoparticles, which can have significant impact on the biological behavior of the proteins and the nanoparticles. We report here on the interactions of iron saturated human transferrin protein with both bare and polyvinyl alcohol coated superparamagnetic iron oxide nanoparticles (SPIONs). The exposure of human transferrin to SPIONs results in the release of iron, which changes the main function of the protein, which is the transport of iron among cells. After removal of the magnetic nanoparticles, the original protein conformation is not recovered, indicating irreversible changes in transferrin conformation: from a compact to an open structure.     

Thermal and mechanical properties of polypropylene/wood‐flour composites

In this research, polypropylene/wood‐flour composites (WPCs) were blended with different contents of wood and/or maleated polypropylene (MAPP) and clay. We found that the addition of MAPP or clay in the formulation greatly improved the dispersion of the wood fibers in the composite; this suggested that MAPP or clay may have played the role of an adhesion promoter in the WPCs. The results obtained with clay indicate that it also acted as a flame retardant. The thermal tests carried out with the produced samples showed an increased crystallization temperature (T_c), crystallinity, and melting temperature (T_m) with wood loading. The increase of the two former parameters was explained by the incorporation of wood flour, which played the role of nucleating agent and induced the crystallization of the matrix polymer. On the other hand, the T_m increase was ascribed to the insulating properties of wood, which hindered the movement of heat conduction. The effects of UV irradiation on T_m and T_c were also examined. T_c increased with UV exposure time; this implied that UV degradation generated short chains with low molecular weight that could move easily in the bulk of the sample and, thus, catalyze early crystallization. The flexural strength and modulus increased with increasing wood‐flour content. In contrast, the impact strength and tensile strength and strain decreased with increasing wood‐flour content. All of these changes were related to the level of dispersion of the wood flour in the polymeric matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and Surface-Active Properties of Uronic Amide Derivatives,Surfactants from Renewable Organic Raw Materials

Short chemical syntheses were developed to produce a new set of surfactants from uronic acids derived from widely available raw materials. Three different strategies were used to synthesize uronic amide derivatives, the structures of which were totally characterized by spectrometric methods (IR, MS, ¹H-RMN and ¹³C-RMN). The best one, using an acid chloride as the synthetic intermediate, furnished the expected amides as a mixture of anomers in 46–58% global yield. Surface-active properties (CMC, γ_cmc, Γ_max, A _min) of homologous series of uronic acid N-alkylamides from C8 to C18 were also assessed. In general, these sugar-based surfactants exhibited good surface-activities, and appeared as valuable nonionic surfactants compared to octylphenol 9–10 ethylene oxide condensate, the most well-known nonionic surfactant. Increasing the alkyl chain length influenced the CMC values for both glucuronic and galacturonic N-alkylamide derivatives. The galacturonic N-alkylamides decreased γ_cmc at slower values than their counterpart’s glucuronic N-alkylamides.