Concurrent effect of microporosity and chemical structure on the equilibrium sorption properties of cellulose-based hydrogels

Polyelectrolite hydrogels are crosslinked polymers which display high sorption capacity in water and water solutions. They are widely used in the marked of personal hygiene products, as well as in other biomedical and industrial applications. In the most industrial application they are not biodegradable and prepared starting from acrylamide.In this work, the chemical-physical analysis of a novel class of natural polymers-based microporous superabsorbent hydrogels has been presented. The main focus is the definition of the relationship between material's chemical-physical structure and its equilibrium sorption properties.The effect of the variation of the degree of crosslinking, the polyelectrolyte nature of the backbone and the hydrogel microporosity on its swelling properties has been analysed, and a good agreement with the theoretical statements has been displayed.The effect of the ionic strength and the pH of the external solution in contact with the hydrogel on its equilibrium sorption properties has also been assessed, and an high sensitivity to these variations was detected for all the tested chemical compositions and physical structures.This work have to be considered part of the efforts towards the reduction of the environmental impact of the large scale consumption industrial polymer based products.     

Rheological evaluation of the influence of polymer concentration and molar mass distribution on the formation and performance of asymmetric gas separation membranes prepared by dry phase inversion

Asymmetric gas separation membranes were prepared by the dry-casting technique from PEEKWC, a modified amorphous glassy poly(ether ether ketone). The phase inversion process and membrane performance were correlated to the properties of the polymer and the casting solution (molar mass, polymer concentration, solution rheology and thermodynamics). It was found that a broad molar mass distribution of the polymer in the casting solution is most favourable for the formation of a highly selective membrane with a dense skin and a porous sub-layer. Thus, membranes with an effective skin thickness of less than 1 μm were obtained, exhibiting a maximum O₂/N₂ selectivity of 7.2 and a CO₂/CH₄ selectivity of 39, both significantly higher than in a corresponding thick dense PEEKWC membrane and also comparable to or higher than that of the most commonly used polymers for gas separation membranes. The CO₂ and O₂ permeance were up to 9.5×10⁻³ and 1.8×10⁻³ m³/(m² h bar) (3.5 and 0.67 GPU), respectively.     

Hydrocarbon decomposition in alumina membrane: an effective way to produce carbon nanotubes bundles

Carbon nanotubes were synthesised within the pores of an alumina membrane. The membrane had 200 nm diameter pores and 60 microm thickness, and ethylene was used as carbon source. Membrane dissolution by HF results in a bundle of parallel open tubes, aligned without macroscopic defects. The external diameter of the tubes is uniform and there is no evidence of any amorphous carbon. Wall thickness control was obtained by varying the reaction time, length by the thickness of alumina membrane, and external tube diameter by the membrane pore size. Scanning (SEM) and transmission (TEM) electron microscopy, atomic force microscopy (AFM), X-ray diffraction, thermogravimetric analysis (TG) and surface area evaluation by nitrogen adsorption were used for the characterization of membrane and nanotubes.     

Crystallization of amorphous indium zinc oxide thin films produced by radio-frequency magnetron sputtering

In this work we studied indium zinc oxide (IZO) thin films deposited by r.f. magnetron sputtering at room temperature. The films were annealed at high temperature (1100 K) in vacuum, and the oxygen exodiffusion was monitored in-situ. The results showed three main peaks, one at approximately 600 K, other at approximately 850 K and the last one at 940 K, which are probably from oxygen bonded in the film surface and in the bulk, respectively. The initial amorphous structure becomes microcrystalline, according to the X-ray diffraction. The electrical conductivity of the films decreases (about 3 orders of magnitude), after the annealing treatment.This behavior could be explained by the crystallization of the structure, which affects the transport mechanism. Apart from the changes in the material structure, a small variation was observed on the absorption coefficient.     

Influence of the layer thickness and hydrogen dilution on electrical properties of large area amorphous silicon p–i–n solar cell

The aim of this work is to present data concerning the optimization of performances of a large area amorphous silicon p–i–n solar cell (30×40 cm²) deposited by plasma enhanced chemical vapour deposition (PECVD) at 27.12 MHz. In this work the solar cell was split into small areas of 0.126 cm², aiming to study the device performance uniformity, where emphasis was put on the role of the n-layer thickness. The solar cells were studied through the spectral response behaviour in the 400–750 nm range as well as by the behaviour of the AC impedance. Solar cells with fill factor of 0.58, open circuit voltage of 0.83 V, short circuit current density of 17.14 mA/cm² and an efficiency of 8% were obtained at growth rates higher than 0.3 nm/s.     

Silicon thin films prepared in the transition region and their use in solar cells

Diphasic silicon films (nc-Si/a-Si:H) have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the nc-Si/a-Si:H has higher photoconductivity (σ_ph), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. The blue shift for the stretching mode and red shift for the wagging mode in the IR spectra also show the variation of the microstructure. By using this kind of film as intrinsic layer, a p–i–n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100 mw/cm²) at room temperature.     

Probing the degree of crosslinking of a cellulose based superabsorbing hydrogel through traditional and NMR techniques

The network structure of a cellulose-based superabsorbing material has been probed by using three different techniques: ¹³C solid state NMR, free swelling in water and uniaxial compression of water swollen samples. A good agreement between the three apporaches has been found in terms of concentration of crosslinks per unit volume.The results have been discussed taking into account that NMR technique is able to detect only chemically effective crosslinks while free swelling and compression are sensitive to elastically effective physical and chemical crosslinks.A depression of swelling capacity and an apparent increase of degree of crosslinking with time, promoted by ageing of the cellulosic material, has been experimentally evidenced and discussed in terms of development of intermolecular physical interactions.     

Crack branching and fracture mirrors in cemented tungsten carbide

Fracture mirrors are investigated in several WC-Co grades with the aim of determining crack branching criteria. The size of the mirrors is found to increase with increasing cobalt content and with decreasing carbide grain size. The results are explained in terms of the dependence on cobalt content and grain size of the free surface energy and the elastic strain at fracture.     

Introduction of molecular spacers between the crosslinks of a cellulose‐based superabsorbent hydrogel: Effects on the equilibrium sorption properties

The possibility to modulate cellulose‐based hydrogel sorption properties through the insertion of molecular spacers between the crosslinks was investigated. Starting polymers were the sodium salt of carboxymethyl cellulose, a polyelectrolyte cellulose derivative, and hydroxyethyl cellulose, a nonpolyelectrolyte derivative. Poly(ethylene glycol) with various molecular weights was linked by its free ends at two divinyl sulfone (DVS) crosslinker molecules, to increase the average distance between two crosslinking sites and thus to act as a spacer. Both the effect of the concentration and the molecular weight of the spacer on the hydrogel final sorption properties in water and water solutions were investigated. The presence of the spacer allowed us also to perform hydrogel synthesis with higher concentrations of cellulose in the reactive mixture, and the effect of the polymer concentration in the batch was analyzed. Hydrogels obtained in the presence of spacers displayed significantly higher equilibrium sorption properties than those of the ones obtained without spacers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 168–174, 2003     

Remediation of waters contaminated with ionic herbicides by sorption on polymerin

This study investigated the sorption of paraquat and 2,4-D on polymerin, the humic acid-like fraction of olive mill wastewater. Effects of pH, contact time, initial concentration and sorbent dosage on the sorption of both herbicides were studied. The sorption mechanism of paraquat on polymerin was consistent with the ion exchange of this herbicide with Ca, Mg and K natively occurring in the sorbent; in contrast, 2,4-D was bound to polymerin by hydrogen bonding. Simulated wastewaters contaminated with paraquat were purified after three sorption cycles on polymerin renewed at each cycle, at a solid/liquid ratio of 0.5, whereas those containing 2,4-D showed a maximal residue removal of 44% after two sorption cycles at the same ratio. The possible application of this model to other water-soluble herbicides, as well as the possible exploitation of polymerin as a bio-filter for the decontamination of pollution point sources is briefly discussed.