Structure, dynamics and interactions of complex sol-gel hybrid materials through SSNMR and DSC: Part II, ternary systems based on PE-PEG block copolymer, PHS and silica

This work is the second part of a study aimed at understanding in more depth structure, dynamics, interactions and correlations between morphology and barrier properties against oxygen diffusion of complex PE-PEG/PHS/SiO₂ hybrids prepared through a sol-gel process. Using a combined DSC and solid-state NMR approach, including ¹³C and ²⁹Si experiments and ¹H ultra-fast MAS spectra, the structural, phase and interaction properties of three PE-PEG/PHS/SiO₂ samples with different compositions, exhibiting different barrier performances, have been investigated, also taking into account the results obtained for the simpler one- and two-component systems (Part I). While the structure of the silica domains has been found to be not affected by composition, many differences have been observed concerning the phase and dynamic properties of the organic components (PE and PEG crystallinity and mobility of their amorphous domains) and the inter-component interactions (strength of the hydrogen bonds between PHS and both silica and PEG and PHS/PEG miscibility). In particular peculiar phase and interaction properties of the sample exhibiting the best barrier properties have been identified and characterized.     

Structural-microstructural characterization and optical properties of Eu3+,Tb3+-codoped LaPO4·nH2O and LaPO4 nanorods hydrothermally synthesized with microwaves

Rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄·nH₂O single-crystal nanorods with the compositions La_0.99999-xEu_xTb_0.00001PO₄·nH₂O (x?=?0–0.03), La_0.99999-yTb_yEu_0.00001PO₄·n′H₂O (y?=?0–0.010), and La_0.99999-zTb_zEu_0.000007PO₄·n′′H₂O (z?=?0–0.012) were hydrothermally synthesized with microwaves. It is shown that the Eu³⁺,Tb³⁺ codoping does not affect the thermal stability of these nanorods, which is due to the formation of substitutional solid solutions with both Eu³⁺ and Tb³⁺ replacing La³⁺ in the crystal lattice. Moreover, it is also shown that monazite-type Eu³⁺,Tb³⁺-codoped LaPO₄ single-crystal nanorods can be obtained by calcining their rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄·(n,n′ or n′′)H₂O counterparts at moderate temperature in air, and that they are thermally stable. It is also observed that, for the same Eu³⁺,Tb³⁺-codoping content, the monazite-type Eu³⁺,Tb³⁺-codoped LaPO₄ nanorods exhibit higher photoluminescent efficiency than the rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄· (n,n′ or n′′)H₂O nanorods. Moreover, it is found that the highest photoluminescence emission corresponds to the monazite-type La_0.96999Eu_0.02Tb_0.00001PO₄ nanorods for the La_0.99999-xEu_xTb_0.00001PO₄ system. However, for those compositions energy transfer from Tb³⁺ to Eu³⁺ does not occur. In addition, for an efficient energy transfer to occur, a content of at least 1?mol% Tb³⁺ is needed in all the studied materials.     

Nanodiamond-mediated crystallization in fibers of PANI nanocomposites produced by template-free polymerization: Conductive and thermal properties of the fibrillar networks

The detonation nanodiamond is a novel versatile nanomaterial with tunable properties and surface chemistry. In this work, we report on a template-free method to synthesize polyaniline based nanocomposite fibers during a chemical oxidative precipitation polymerization where the cooperative interactions between nanodiamond and polyaniline nucleates trigger the final morphology of the nanocomposite. FE–SEM and TEM observations evidence the prominent growth of fibril-like structures assembled in 2-D networks of tightly woven, partially oriented fibers. Optical and Raman spectroscopy and X-ray diffraction analyses reveal that the polymer chains are in a protonated emeraldine form and organize themselves in a highly ordered 3-D spatial arrangement. Conductivity measurements performed on isolated fibers by a conductive tip of an AFM apparatus highlight that the diamond filler does not affect the conductive properties of the polyaniline matrix while increases the thermal stability of the polymer as confirmed by TGA studies.     

Effect of a new fermented soy milk product on serum lipid levels in normocholesterolemic adult men

This study was undertaken to verify the effect of a daily intake of a new fermented soy milk produced with Enterococcus faecium and Lactobacillus jugurti on the serum lipid levels in normocholesterolemic middle-aged men. The study was randomized, double-blind and placebo-controlled and was performed for a period of 6 weeks. Forty-four normocholesterolemic healthy, male volunteers, aged 40-55 years old were randomly separated in two groups: The F-group received 200 ml of the fermented product daily and the P-group received 200 ml of placebo (chemically fermented). The blood samples were drawn initially and after 3 and 6 weeks and serum values for total cholesterol, HDL-cholesterol and triglyceride were determined. The LDL-cholesterol value was estimated. No significant changes in the fermented group (F) were observed for total cholesterol, LDL-cholesterol or triglyceride levels, while the HDL-cholesterol level was significantly higher (p < or = 0.05) after 6 weeks. The total cholesterol and LDL-cholesterol levels were significantly higher (p < or = 0.05) in the placebo group (P), but no changes were found for the HDL-cholesterol and triglyceride levels during the experimental period. In conclusion, the intake of 200 ml/day of the fermented soy milk, produced with E. faecium and L. jugurti, for 6 weeks, did not affect the serum total cholesterol and LDL-cholesterol, and led an increase of 10% in the HDL-cholesterol level.     

Screening of Soluble Rhodium Nanoparticles as Precursor for Highly Active Hydrogenation Catalysts: The Effect of the Stabilizing Agents

We report the preparation of rhodium nanoparticles (NPs) stabilized by 1-octadecanethiol (ODT), polyvinyl alcohol (PVA), and tetraoctylammonium bromide (TOAB), and their application for hydrogenation catalysis. The three metal–ligand systems correspond to different mechanism of NPs stabilization via strong covalent linkage, chemisorbed atoms and electrostatic interactions, respectively. We found a strong effect of the interaction between the stabilizer and the surface of the metal nanoparticle on the catalytic activity. The Rh NPs were studied as soluble nanoparticle catalysts and as precursors for the synthesis of supported catalysts. All catalysts were tested in the hydrogenation of cyclohexene under similar conditions as a model reaction. Generally, Rh–ODT NPs were inactive, Rh–PVA NPs exhibited distinct activities in solution (aqueous biphasic catalysis) and as a supported catalyst, and Rh–TOAB NPs exhibited similar activities in solution and after immobilization. This last result opens the opportunity for the preparation of highly active Rh NP catalysts both in solution and as a heterogeneous catalyst. Additionally, the stability of the nanoparticles depends on the choice of ligand and on the functionalization of the support surface before immobilization. By optimizing the catalyst synthesis and reaction conditions, turnover frequencies as high as 700,000 h^?1 where observed for stable and recyclable catalyst.     

Aggregation Behavior of Perfluorononanoic Acid/Sodium Dodecyl Sulfate Mixtures

The mixed system of an anionic hydrocarbon surfactant, sodium dodecyl sulfate, and a perfluorinated surfactant, perfluorononanoic acid (PFNA), was investigated by a combination of methods. The critical micellar concentrations (CMC) were determined over a wide range of sample compositions by surface tension, conductivity and UV–visible spectrophotometry using N-(4-nitrophenyl)perfluorononanamide as a molecular probe. The values of CMC obtained by different techniques were in good agreement. In addition, the aggregation numbers were determined in the mixtures with a low content of hydrocarbon surfactant, by measuring the fluorescence quenching of pyrene. The hydrodynamic radii of the aggregates were estimated through the diffusion ordered ¹⁹F- and ¹H-NMR spectroscopy. The values obtained are in agreement with those expected according to the measured aggregation numbers. The analysis of the data with different aggregation models suggests the formation of a non-ideal mixed micelle that is enriched in the perfluorinated surfactant when its mole fraction increases, and that is practically formed by PFNA only at mole fractions higher than 0.8.     

Impact of tire debris on in vitro and in vivo systems

Background  

It is estimated that over 80% of respirable particulate matter (PM₁₀) in cities comes from road transport and that tire and brake wear are responsible for the 3–7% emission of it. Data on the indicators of environmental impact of tire debris (TD), originated from the tire abrasion on roads, are extremely scarce, even though TD contains chemicals (zinc and organic compounds) which can be released in the environment.     

Metal sols as a useful tool for heterogeneous gold catalyst preparation: reinvestigation of a liquid phase oxidation

Differently stabilised metal sols have been used as precursors in the preparation of heterogeneous gold catalysts for liquid phase oxidation in water solution. The methodology of sols generation appears to be fundamental to obtaining nanoparticles; the support, instead, plays an important role in maintaining particle dimension and morphology.

Three different materials (γ-Al₂O₃, SiO₂ and activated carbon) have been used as the supporting agents for different gold sols that were obtained by reducing HAuCl₄ with NaBH₄ in the presence of polyvinylalcohol (PVA) or polyvinylpirrolidone (PVP) and with the tetrakis(hydroxymethyl)phosphonium chloride (THPC)/NaOH system. During the immobilisation step, the maintenance of the particle dimension observed in solution depends on both the support and the type of sol. The gold particle mean size of the colloidal suspension is more easily maintained on oxidic supports than on carbon, the latter apparently needing both steric and polar stabilisation of the gold particle.

Comparison of Au/γ-Al₂O₃ and Au/C catalyst activity in the liquid phase oxidation of ethylene glycol to glycolate highlighted the peculiarity of gold on carbon catalysts; in fact, the normally observed trend of reactivity is partially reversed, medium sized gold particle being the most active.     

Superlattices as Characterisation Tool for the Beginning of PS Formation

Initial stage of porous silicon (PS) formation has been studied in an original way. Multilayer structures constituting of very thin layers of low porosity and thick layers of high porosity have been fabricated and characterised by optical tools and electron microscopy. The non linear behaviour resulting in a change in the dissolution velocity has been quantified by using a stack layer structure. Finally using thermal oxidation it has been shown that, due to the selective oxidation as a function of the porosity, porous silicon can be used to produce a Si/SiO₂ like structure.     

Advanced testing procedures for high performance coatings

In the first part of this work, an integrated approach incorporating electrochemical (electrochemical impedance spectroscopy), calorimetric (differential scanning calorimetry), mechanical (dynamic mechanical thermal analysis), and infrared spectroscopy (Fourier transform infrared spectroscopy) techniques was used to characterize some organic coatings from the automotive industry. Comparison of the results obtained with different techniques allows not only a higher precision in the evaluation of natural or artificial degradation, which is very difficult to obtain using traditional techniques, but also better data interpretation and, therefore, the possibility of understanding the different degradation mechanisms. In the second part, some preliminary results concerning the comparison of salt spray exposure and EIS measurements are discussed. The statistical analysis of the results showed that the degradation mechanism in the two cases is completely different and, therefore, the information which is obtained with the two testing approaches is also different. With EIS measurements obtained in immersion, it is possible to monitor, in particular, the barrier properties of the coatings, which are dominated by the presence of defects. In the case of salt spray (without scratch), the main property to be measured is the loss of adhesion which causes blister formation. Presented at the 77th Annual Meeting of the Federation of Societies for Coatings Technology, on October 18–22, 1999, in Dallas, TX. Dept. of Materials Engineering, Via Mesiano 77, Trento, Italy. e-mail: Flavio.Deflorian@ing.unitn.it; Stefano.Rossi@ing.unitn.it; Bonora@ing.unitn.it. Dept. ICMMPM, Via Eudossiana, Rome, Italy. e-mail: Lorenzo.Fedrizzi@ing.unitn.it.