0000000000042901
AUTHOR
D. Chillura Martino
Localization of n-alcohols and structural effects in aqueous solutions of sodium dodecyl sulfate
Small-angle neutron Mattering measurements OD sodium dodecyl sulfate aqueous solutions have been performed in the presence of n-alcohols, from methanol to octanol, at different alcohol concentrations. By modeling the experimental intensities, it was possible to obtain structural information and to derive simultaneously the distribution of the alcohols between the aqueous and the micellar phases. It was found that short chain alcohols tend to remain in the aqueous phase and, by altering the solvent properties, induce a decrease in the aggregation number of sodium dodecyl sulfate micelles. On the other hand, alcohols with longer hydrocarbon chains were found to be present in both phases thoug…
H and 19F NMR Investigation on Mixed Hydrocarbon−Fluorocarbon Micelles
1H and 1 9 F NMR measurements on aqueous solutions of sodium perfluorooctanoate (SPFO) and sodium dodecanoate (SD) mixtures are reported. The surfactant concentration ranged from ∼0.3 to 10 times the critical micelle concentration (cmc ≅ 0.03 mol L - 1 ). The cmc of the SD/SPFO/water mixed system obtained from NMR data was in good agreement with that previously obtained by conductivity measurements. Below the cmc, the experimental chemical shift (δ) was independent of the total concentration for both surfactants. Above the cmc, however, the 6 values for 1 9 F varied linearly with concentration, whereas the values for the hydrogenated surfactant deviated from linearity. These observations in…
The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of polycarbonate
Abstract Polycarbonate/silica nanocomposites with different silica quantities were prepared by a melt compounding method. The effect of silica amount, in the range 1–5 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of polycarbonate (PC) was investigated. Clusters of silica nanoparticles were well dispersed in the polycarbonate whose structure remained amorphous. NMR results showed intermolecular interactions involving the carbonyl groups of different polymeric chains which did not affect the intramolecular rotational motions. The presence of the lowest silica content showed a decrease in the storage and loss moduli below the glass transition temperature, pro…
Photochemical synthesis of pyrene perfluoroalkyl derivatives and their embedding in a polymethylmethacrylate matrix: a spectroscopic and structural study
A photochemical, alternative and eco-compatible approach to perfluoroalkyl derivatives of pyrene is presented. The perfluoroalkyl chain is regiospecifically introduced at the 1 position of pyrene. The synthesized products have been embedded in a polymethylmethacrylate matrix by photocuring at 365 nm. Both the photochemical reactions can be considered a “green tool” for the synthetic chemist in order to obtain materials with prospective optoelectronic applications. The so-obtained composites have been the object of a study by UV and fluorescence spectroscopy in order to explore their luminescence properties. The small angle X-ray scattering and the transmission electron microscopy techniques…
Influence of the modification, induced by zirconia nanoparticles, on the structure and properties of polycarbonate
Melt compounding was used to prepare polycarbonate (PC)–zirconia nanocomposites with different amounts of zirconia. The effect of the zirconia loading, in the range of 1–5 wt.%, on the structure, mechanical properties and thermal degradation kinetics was investigated. The zirconia nanoparticle aggregates were well dispersed in the PC matrix and induced the appearance of a local lamellar order in the polycarbonate as inferred by SAXS findings. This order could be a consequence of the intermolecular interactions between zirconia and the polymer, in particular with the quaternary carbon bonded to the methyl groups and the methyl carbon as inferred from the NMR results. The presence of zirconia…
Determination of the Composition of Mixed Hydrogenated and Fluorinated Micelles by Small Angle Neutron Scattering
Molecular association of cryptand 221D in NaCl-water solutions. A small-angle neutron scattering study
Molecules of 5-Decyl-4,7,13,16,21-pentaoxa-1,10-diaza-bicyclo-[8.8.5.]tricosan (221D) and its sodium complex, with both a hydrophobic and a hydrophilic portion, are expected to form aggregates in water solutions. This was confirmed by surface tension measurements. The aggregation behaviour was studied by small-angle neutron scattering at two different [NaCl]/[221D] molar ratios, such as to obtain, in one case, aggregates entirely made up of ionic monomers, and in the other, mixed micelles constituted by both ionic and non-ionic units. The variation of the aggregation number and number of aggregates indicated that, in the former case, smaller micelles were formed, as a consequence of repulsi…
Structural Characterization of Zirconia Nanoparticles Prepared by Microwave-Hydrothermal Synthesis
Nanocrystalline zirconia powders have been prepared by microwave-hydrothermal synthesis starting from aqueous solution of ZrOCl2·8H2O. Results of investigations on the aqueous suspension stability of the washed zirconia nanopowders by dynamic light scattering showed that the suspension, constituted by superaggregates of nanoparticles (131 ± 10 nm), was stable up to 15 days. Nanopowders were investigated by means of transmission electron microscopy and small angle x-ray scattering measurements which proved that the zirconia nanopowder is constituted by small primary nanoparticles of ca. 8 nm that agglomerate forming bigger aggregates of 50 ± 1 nm.
Synthesis, size control, and passivation of CdS nanoparticles in water/AOT/n-heptane microemulsions
Abstract CdS nanoparticles have been synthesised by adding tetrabutylammonium hydrogen sulphide to water/sodium bis(2-ethylhexyl) sulfosuccinate/ n -heptane microemulsions containing CdSO 4 . Analysis of UV–Vis absorption spectra recorded at various times indicates that an initial rapid formation of CdS nanoparticles is followed by a very slow growth process which can be well described by a power law. The growth process is totally inhibited by the addition of an appropriate amount of bis(2-ethylhexyl)amine (BEA) leading to the formation of stable nanosized CdS particles coated by an oriented monolayer of chemically bonded BEA molecules. Depending on the BEA addition time, the growth inhibit…
Experimental investigation and modeling of diffusion dialysis for HCl recovery from waste pickling solution
Abstract Hydrochloric acid recovery from pickling solutions was studied by employing a batch diffusion dialysis (DD) laboratory test-rig equipped with Fumasep membranes. The effect of main operating parameters such as HCl concentration (0.1–3 M) and the presence of Fe2+ (up to 150 g/l) was investigated to simulate the system operation with real industrial streams. The variation of HCl, Fe2+ and water flux was identified. When only HCl is present, a recovery efficiency of 100% was reached. In the presence of FeCl2, higher acid recovery efficiencies, up to 150%, were observed due to the so-called “salt effect”, which promotes the passage of acid even against its concentration gradient. A 7% l…
Application of the small-angle neutron scattering technique to the study of solubilization mechanisms of organic molecules by micellar systems
Abstract We present the possible contribution of the small-angle neutron scattering (SANS) technique to the molecular interpretation of the solubilization phenomena in simple micellar systems. We show for a few ternary micellar systems, that an appropriate analysis of SANS experimental data can provide information on modifications induced on micellar dimension, shape, number of monomer, and charge and on the partition coefficient of the additive and its localization inside the micellar aggregate. The influence of n -alcohols on the thermodynamics and on the structure of sodium dodecyl sulphate (SDS) aqueous solution has been extensively investigated, so the agreement between the results obt…
Superhydrophobic TiO2/Fluorinated Polysiloxane Hybrid Coatings with Controlled Morphology for Solar Photocatalysis
Abstract Technological applications of polysiloxane coatings have been influenced by their intrinsic low surface energy, which increases their water repellence. Accurate control of composition and interfacial properties through the introduction of perfluorinated moieties further lowers the polysiloxane surface energy, while mixing with metal oxide nanoparticles enhances roughness, resulting in a great potential in the development of superhydrophobic materials for photocatalysis. Herein, a series of hydrophobic and superhydrophobic hybrid coatings were prepared by dehydrocoupling and hydrosilylation reactions of polymethylhydrosiloxane with 1H,1H,2H,2H‐perfluorooctyltriethoxysilane and 1,3-d…
FT-IR and dielectric study of water/AOT liquid crystals
Abstract In order to explore the influence of microwave radiation on highly viscous microheterogeneous systems, the evolution of structural and dynamical properties of the water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT) liquid crystals as a function of the molar ratio R (R=[water]/[AOT]) has been investigated by FT-IR spectroscopy and time domain reflectometry. The study emphasises how the progressive hydration of the surfactant head groups is mainly responsible for the structural and dynamical evolution of water/AOT liquid crystals. In particular, it has been found that the state of water at lower R values is strongly perturbed, bulk-like water appears only at R>23 and the water/AOT in…
Luminescence properties of neodymium-doped yttrium aluminium garnet obtained by the co-precipitation method combined with the mechanical process
Nanopowders of yttrium aluminium garnet Y3Al5O12 (YAG) doped with neodymium ions were obtained by the co-precipitation method from the reaction of aluminium and yttrium nitrate and neodymium oxide with ammonia. After washing and drying the hydroxide precursors were calcined at 500, 700, 800 and 900 °C for 1 hour and at 1000 °C for 3 hours. This product was treated by ball milling in a zirconia vial for 0.5, 1.5 and 10 h in order to achieve smaller nanoparticles. The structure, microstructure, morphology and optical properties were investigated by means of diffractometric, microscopic and spectroscopic techniques. The course of the amorphous-to-crystalline transformation was complete after c…
MCM-41-CdS nanoparticle composite material: Preparation and characterization
The preparation and characterization of a hierarchical material constituted by a mesoporous silica MCM-41 whose mesochannels contain CdS nanoparticles capped with both bis(2-ethylhexyl) amine and bis(2-ethylhexyl) sodium sulfosuccinate is reported. MCM-41 powder was synthesized by using the LCT methodology. CdS nanoparticles were obtained within the inversed micelle core of a water/ AOT/n-heptane microemulsion. Nanoparticles growth was followed by means of UV–Vis spectroscopy and was inhibited by BEA addition. The CdS-capped nanoparticles were separated by centrifugation, washed with water and ethanol and finally dispersed in n-heptane. The insertion of CdS nanoparticles into MCM-41 mesocha…
An automatic L1-based regularization method for the analysis of FFC dispersion profiles with quadrupolar peaks
Fast Field-Cycling Nuclear Magnetic Resonance relaxometry is a non-destructive technique to investigate molecular dynamics and structure of systems having a wide range of ap- plications such as environment, biology, and food. Besides a considerable amount of liter- ature about modeling and application of such technique in specific areas, an algorithmic approach to the related parameter identification problem is still lacking. We believe that a robust algorithmic approach will allow a unified treatment of different samples in several application areas. In this paper, we model the parameters identification problem as a con- strained L 1 -regularized non-linear least squares problem. Following…
FFC-NMR Relaxometric Characterization of Nanosponges for Rationalizing their Adsorption and Release abilities
Small angle scattering study of the structure of isotactic polypropylene-hydrogenated oligo(cyclopentadiene) blends
Abstract Blends of isotactic polypropylene ( i PP) and hydrogenated oligo cyclopentadiene (HOCP) have been studied by means of small angle X-ray scattering in the temperature range 70–160°C. The structure of blends containing less than 25% HOCP is very similar to the one of plain i PP, i.e. lamellae whose thickness increases by increasing the temperature. Blends containing more than 25% HOCP are characterized by two kinds of lamellae formed by layers of i PP and amorphous material rich in i PP and in HOCP, respectively. The crystallizable i PP present in both phases crystallizes from the melt, in analogy to what happens in HDPE/HOCP blends and in agreement with the values of the crystallini…