Frédéric Bouyer

Hydrophilic block copolymer-directed growth of lanthanum hydroxide nanoparticles

Stable hairy lanthanum hydroxide nanoparticles were synthesized in water by performing hydrolysis and condensation reactions of lanthanum cations in the presence of double hydrophilic polyacrylic acid-b-polyacrylamide block copolymers (PAA-b-PAM). In the first step, the addition of asymmetric PAA-b-PAM copolymers (Mw,PAA < Mw,PAM) to lanthanum salt solutions, both at pH = 5.5, induces the formation of monodispersed micellar aggregates, which are predominantly isotropic. The core of the hybrid aggregates is constituted of a lanthanum polyacrylate complex whose formation is due to bidentate coordination bonding between La3+ and acrylate groups, as shown by ATR-FTIR experiments and pH measurements. The size of the micellar aggregates depends on the molecular weight of the copolymer but is independent of the copolymer to metal ratio in solution. In the second step, the hydrolysis of lanthanum ions is induced by addition of a strong base such as sodium hydroxide. Either flocculated suspensions or stable anisotropic or spherical nanoparticles of lanthanum hydrolysis products were obtained depending on the metal complexation ratio [acrylate]/[La]. The variation of that parameter also enables the control of the size of the core-corona nanoparticles obtained by lanthanum hydroxylation. The asymmetry degree of the copolymer was shown to influence both the size and the shape of the particles. Elongated particles with a high aspect ratio, up to 10, were obtained with very asymmetric copolymers (Mw,PAM/Mw,PAA ≥ 10) while shorter rice grain-like particles were obtained with a less asymmetric copolymer. The asymmetry degree also influences the value of the critical metal complexation degree required to obtain stable colloidal suspensions of polymer-stabilized lanthanum hydroxide.

Hybrid Polyion Complex Micelles Formed from Double Hydrophilic Block Copolymers and Multivalent Metal Ions: Size Control and Nanostructure

Hybrid polyion complex (HPIC) micelles are nanoaggregates obtained by complexation of multivalent metal ions by double hydrophilic block copolymers (DHBC). Solutions of DHBC such as the poly(acrylic acid)-block-poly(acrylamide) (PAA-b-PAM) or poly(acrylic acid)-block-poly(2-hydroxyethylacrylate) (PAA-b-PHEA), constituted of an ionizable complexing block and a neutral stabilizing block, were mixed with solutions of metal ions, which are either monoatomic ions or metal polycations, such as Al(3+), La(3+), or Al(13)(7+). The physicochemical properties of the HPIC micelles were investigated by small angle neutron scattering (SANS) and dynamic light scattering (DLS) as a function of the polymer block lengths and the nature of the cation. Mixtures of metal cations and asymmetric block copolymers with a complexing block smaller than the stabilizing block lead to the formation of stable colloidal HPIC micelles. The hydrodynamic radius of the HPIC micelles varies with the polymer molecular weight as M(0.6). In addition, the variation of R(h) of the HPIC micelle is stronger when the complexing block length is increased than when the neutral block length is increased. R(h) is highly sensitive to the polymer asymmetry degree (block weight ratio), and this is even more true when the polymer asymmetry degree goes down to values close to 3. SANS experiments reveal that HPIC micelles exhibit a well-defined core-corona nanostructure; the core is formed by the insoluble dense poly(acrylate)/metal cation complex, and the diffuse corona is constituted of swollen neutral polymer chains. The scattering curves were modeled by an analytical function of the form factor; the fitting parameters of the Pedersens model provide information on the core size, the corona thickness, and the aggregation number of the micelles. For a given metal ion, the micelle core radius increases as the PAA block length. The radius of gyration of the micelle is very close to the value of the core radius, while it varies very weakly with the neutral block length. Nevertheless, the radius of gyration of the micelle is highly dependent on the asymmetry degree of the polymer: if the neutral block length increases in a large extent, the micelle radius of gyration decreases due to a decrease of the micelle aggregation number. The variation of the R(g)/R(h) ratio as a function of the polymer block lengths confirms the nanostructure associating a dense spherical core and a diffuse corona. Finally, the high stability of HPIC micelles with increasing concentration is the result of the nature of the coordination complex bonds in the micelle core.

Brittle creep and subcritical crack propagation in glass submitted to triaxial conditions

An experimental work is presented that aimed at improving our understanding of the mechanical evolution of cracks under brittle creep conditions. Brittle creep may be an important slow deformation process in the Earths crust. Synthetic glass samples have been used to observe and document brittle creep due to slow crack-propagation. A crack density of 0.05 was introduced in intact synthetic glass samples by thermal shock. Creep tests were performed at constant confining pressure (15 MPa) for water saturated conditions. Data were obtained by maintaining the differential-stress constant in steps of 24 h duration. A set of sensors allowed us to record strains and acoustic emissions during creep. The effect of temperature on creep was investigated from ambient temperature to 70°C. The activation energy for crack growth was found to be 32 kJ/mol. In secondary creep, a large dilatancy was observed that did not occur in constant strain rate tests. This is correlated to acoustic emission activity associated with crack growth. As a consequence, slow crack growth has been evidenced in glass. Beyond secondary creep, failure in tertiary creep was found to be a progressive process. The data are interpreted through a previously developed micromechanical damage model that describes crack propagation. This model allows one to predict the secondary brittle creep phase and also to give an analytical expression for the time to rupture. Comparison between glass and crystalline rock indicates that the brittle creep behavior is probably controlled by the same process even if stress sensitivity for glass is lower than for rocks.

Evolution of the crack network in glass samples submitted to brittle creep conditions

A crack network is introduced in glass by quenching heated samples. The sharp variation of temperature at the sample boundaries leads to tensile stresses that nucleate cracks. Then, they propagate in the entire sample. Quenching has been performed at 100, 200 and

Computational Chemistry: A Way To Reach Spectroscopic and Thermodynamic Data for Exotic Compounds

300\,^\circ \hbox {C}

Aggregation of Colloidal Particles in the Presence of Oppositely Charged Polyelectrolytes: Effect of Surface Charge Heterogeneities

300∘C. Cracks have been imaged with a scanning electron microscope. A transverse isotropic crack network is observed. Crack length and orientation have been measured. Obtained crack density has been compared to that inferred from elastic wave velocity measurements using effective medium theory. Cracked samples have been then submitted to creep tests. Two samples have been recovered, one before its failure and another after. Our observations show that vertical crack propagation takes place during brittle creep and that tertiary creep leads to a localized failure in a shear plane. The damaged and post-mortem microstructural networks have been documented.

Cracks in glass under triaxial conditions

DFT calculations were performed in order to acquire structural and energetic informations about aluminum (III) fluoride complexes and their stabilities as a function of the nature of center cation (sodium or calcium). These calculations enable us to explain the stabilizing zffzct of calcium regarding to the four‐ and five‐fold coordinated complexes against the cryolitic anion.

Highly Stable Metal Hydrous Oxide Colloids by Inorganic Polycondensation in Suspension

In this paper, we report a general methodology to reach thermochemical properties of molecules in gas phase. We applied these calculations to related complexes of industrial interest, concerning the electrowinning of aluminum. This thermochemical prediction is a demonstration of a quantitative analysis after geometry optimizations and frequencies calculations from density functional computations (or any first-principle techniques). Since this methodology is completely generic, we can study any complexes of interest in order to study the model of the vapor. We have especially investigated the (Na3AlF6, Na2AlF5, NaAlF4, AlF3, NaF, (NaF)2, (NaAlF4)2) system. It has been found that NaAlF4 and (NaF)2 are the major species present in gas phase. Results concerning calcium are also presented, showing that CaAlF5 is in the vapor. Its partial pressure decreases when the one of CaF2 increases and the partial pressure of NaAlF4 (and all minor species containing aluminum) decreases at the same time.