Rigid polyurethane composite foams were prepared with cellulose fibers as a filler. The cellulose fibers were an industrial residue of blanched cellulose pulp production. The influence of the cellulose fiber concentration on the structural, thermal, mechanical, and morphological properties of the foams was investigated. We also studied the influence of the cellulose fibers on the foam's resistance to fungal attack by placing a suspension of known fungus in contact with the surface of the foam and following the morphological evolution as a function of time (for 60 days). The increase in the cellulose filler concentration in the foams, up to 16% w/w with respect to the polyol, changed their properties as follows: (1) the cell size decreased, (2) the thermooxidative stability and mechanical properties remained approximately constant, (3) the thermal conductivity decreased slightly, and (4) fungal growth was observed. Therefore, a cellulosic fibrous industrial residue was rationally valorized as a filler in classical rigid polyurethane foams; this yielded materials with mechanical resistance and a susceptibility to fungi in a wet environment.
X-ray absorption spectroscopy [extended X-ray absorption fine structure (EX-AFS) and X-ray absorption near-edge structure (XANES)], differential scanning calorimetry, and Raman spectroscopy measurements were performed for a series of liquid polyether/salt systems prepared with poly(tetramethylene glycol) (PTMG) and the copolymer poly(tetramethylene glycol-co-ethylene glycol) as matrices and zinc and cobalt chlorides as dopants in the concentration range of n ϭ 30-90, where n is the molar ratio of oxygen to metal cation. According to EXAFS, XANES, and Raman results, even in diluted solutions, these complexes exist mostly as undissociated ZnCl 2 and CoCl 2 species, presenting a weak cation-polymer interaction. EXAFS results indicate that for polymer/ZnCl 2 systems, the nearest metal neighbors are only chlorine atoms. However, for polymer/CoCl 2 samples, oxygen is also observed coordinating the metal. Raman spectra do not support any feature related specifically to the cation-polymer interaction. Nevertheless, for both salts the symmetric stretching vibrations are located in frequencies characteristic of salt in solution, which means that the polymer solvating action is effective. Differential scanning calorimetry data show an increase in the glass-transition temperature for all polymer/salt systems in relation to the pure polymer samples, a consequence of the increase in the macromolecular chain stiffening produced by the presence of the salt. This result corroborates the existence of polymer-salt interactions.
The dynamic heat capacity and glass-transition temperature of polystyrene (PS)/poly(vinyl acetate-co-butyl acrylate) (VAc-BA) (50:50 w/w) structured latex films as a function of annealing time at 70, 77, and 85°C were examined with modulatedtemperature differential scanning calorimetry. The PS and poly(vinyl acetate-co-nbutyl acrylate) components were considered to be the cores and shells, respectively, in the structured latex. The dynamic heat capacity decreased with time. The glasstransition temperatures of the PS and VAc-BA phases shifted to higher values after annealing. The results of thermogravimetry showed that there existed about 1.8% residual water in the films. The mean free volume and relative concentration of holes at room temperature (before and after annealing) and 85°C, as a function of time, were obtained with positron annihilation lifetime spectroscopy (PALS). The PALS results indicated no significant change in free volume during annealing. It is believed that the loss, by diffusion, of residual water mainly caused a decrease in heat capacity and an increase in the glass-transition temperatures. As little as 1.8% residual water in the structured latex films had a significant influence on the thermal properties.
Composites of alumina ceramic powders prepared by co-precipitation and sol-gel methods with Lithium Iodide based polymer electrolytes are described. The polyether matrices Poly(ethylene oxide) (PEO) and block copolymer Poly(propylene glycol-ethylene glycolpropylene glycol) (Triblock) with Lil in a ratio [O]:[Li] = 20:1 are used with up to 17 wt% of α-A1203 (medium grain size). Differential Scanning Calorimetry (DSC) studies show that Tg values for PEO based composites are higher whereas those for Triblock based composites are lower than the Tg value of the polymer/salt system.Conductivity measurements as a function of temperature show that there is no significant change in conductivity above the melting points for the electrolytes after α-A1203 powder addition (σ approximately 10−3 S.cm−l at 100°C), whereas better mechanical properties are observed for the ceramic reinforced samples. An increase in conductivity is obtained for the Triblock based composites near room temperature as a consequence of the lower melting point of these materials (26°C) in comparison to the PEO based composites (54°C).
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