Analysis of Poly(thiourethane) Covalent Adaptable Network through Broadband Dielectric Spectroscopy.

The dielectric spectra of the poly(thiourethane) network, HDI-S3, have been analyzed to know the nature and the cooperativity of each of the six dielectric processes observed. At low temperatures, γ1, γ2, and ß dielectric relaxations were attributed to noncooperative local motions in the glassy state, in which apparent activation energies are 30, 36, and 60 kJ·mol-1, respectively. At higher temperatures, three dielectric relaxations are observed (αTg, α*, ρ). The αTg relaxation is attributed to the glass transition, and it is overlapped with the α* relaxation. The molecular origin of α* relaxation is associated with the bond exchange reaction. Finally, the ρ relaxation is ascribed to the heterogeneity of the sample although its origin is uncertain. The DC conductivity (σDC) is found to be an appropriate variable to analyze the bond exchange reaction. Accordingly, the HDI-S3 has a molecular exchange mechanism of dissociative nature.

Dielectric Properties in Oriented and Unoriented Membranes Based on Poly(Epichlorohydrin-co-Ethylene Oxide) Copolymers: Part III.

The dielectric spectra and conductivity properties of neat poly(epichlorohydrin-co-ethylene oxide)(PECH-co-EO) copolymer and two modified copolymers with a 20% or 40% of dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate units were analysed. A process of thermal orientation was applied to the copolymers to fine-tune the molecular motion of the side chains and determine their validity for cation transport materials. The study was conducted using Dielectric Thermal Analysis (DETA). The spectra of the modified unoriented and oriented copolymers consisted of five dielectric relaxations (δ, γ, ß, αTg, and αmelting). The analysis of the relaxations processes shows that as the grafting with the dendron units increases, both the lateral and main chains have a greater difficulty moving. The thermal orientation induces in the main chain partial crystallization, including the polyether segments, and modifies the cooperative motion of the main chain associated with the glass transition (αTg). A deep analysis of the electrical loss modulus revealed that the degree of modification only modifies the temperature peak of each relaxation, and this effect is more perceived if the dendron unit content is higher (40%). The thermal orientation process seems equal to the spectra of CP20-O and CP40-O to the point that the degree of modification does not matter. Nevertheless, the fragility index denotes the differences in the molecular motion between both copolymers (40% and 20%) due to the thermal orientation. The study of the electric conductivity showed that the ideal long-range pathways were being altered by neither the thermal orientation process nor the addition of dendrimers. The analysis of the through-plane proton conductivity confirmed that the oriented copolymer with the highest concentration of dendrimers was the best performer and the most suitable copolymer for proton transport materials.

New silica based adsorbent material from rice straw and its in-flow application to nitrate reduction in waters: Process sustainability and scale-up possibilities.

This paper shows a particular example to move to a sustainable circular economical process from valorization of rice straw ashes by developing a green synthesis for obtaining a useful sub-product. This strategy can palliate negative effects of the agriculture waste practices on the environment and also the obtained silica reduced nitrate content in waters. It is demonstrated that the silica synthesis developed at lab was scalable more than a hundred times with good results. Adsorption studies of nitrate in standards and real well waters at lab scale and scaling-up provided similar results. Adsorption values near to 15 mg/g for nitrate standards and 8.5 mg/g for well water were obtained until achieving the initial nitrate concentration. Experimental breakthrough curves fitted to Thomas model, which gave similar results for adsorption capacities. The adsorption capacity was checked with that obtained by a commercial resin, providing improved results. The method at large scale was compared with industrial traditional methods and green adsorbents.

Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers.

The macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers show an ability to change their shape, achieve orientation, and slightly crystallize, which was also observed by CP-MAS NMR, XRD, and DSC. The phenomenon was deeply analyzed by dielectric thermal analysis. The dielectric spectra show the influence of several factors such as the number of dendritic side groups, the orientation, their self-assembling dendrons, and the molecular mobility. The dielectric spectra present a sub-Tg dielectric relaxation, labelled as γ, associated with the mobility of the benzyloxy substituent of the dendritic group. This mobility is not related to the percentage of these lateral chains but is somewhat hindered by the orientation of the dendritic groups. Unlike other less complex polymers, the crystallization was dismantled before the appearance of the glass transition (αTg). Only after that, clearing transition (αClear) can be observed. The PECHs were flexible and offered a high free volume, despite presenting a high degree of modifications. However, the molecular mobility is not independent in each phase and the self-assembling dendrons can be eventually fine-tuned according to the percentage of grafted groups.

Encapsulation of Vitamins A and E as Spray-Dried Additives for the Feed Industry.

Encapsulated fat-soluble powders containing vitamin A (VA) and E (VE) were prepared as a feasible additive for extruded feed products. The effect of the encapsulating agents (Capsul-CAP®, sodium caseinate-SC) in combination with Tween 80 (TW) as an emulsifier and maltodextrin (MD) as a wall material on the physicochemical properties of emulsions and powders was evaluated. First, nanoemulsions containing MD:CAP:TW:VA/VE and MD:SC:TW:VA/VE were prepared and characterized. Then, powders were obtained by means of spray-drying and analyzed in terms of the product yield, encapsulation efficiency, moisture content, porosity, surface morphology, chemical structure, and thermal properties and thermo-oxidative/thermal stability. Results showed that although nanoemulsions were obtained for all the compositions, homogeneous microcapsules were found after the drying process. High product yield and encapsulation efficiency were obtained, and the presence of the vitamins was corroborated. The characteristics of the powders were mainly influenced by the encapsulating agent used and also by the type of vitamin. In general, the microcapsules remained thermally stable up to 170 °C and, therefore, the proposed encapsulation systems for vitamins A and E were suitable for the preparation of additives for the feed manufacturing through the extrusion process.

Polycaprolactone/gelatin-based scaffolds with tailored performance: in vitro and in vivo validation.

Nanofibrous scaffolds composed of polycaprolactone (PCL) and gelatin (Ge) were obtained through a hydrolytic assisted electrospinning process. The PCL-to-Ge proportion (100/0 to 20/80), as well as the dissolution time (24, 48, 72, 96, 120 h) into a 1:1 formic/acetic acid solvent before electrospinning were modified to obtain the different samples. A strong influence of these factors on the physicochemical properties of the scaffolds was observed. Higher Ge percentage reduced crystallinity, allowed a uniform morphology and increased water contact angle. The increase in the dissolution time considerably reduced the molar mass and, subsequently, fibre diameter and crystallinity were affected. During in vitro biocompatibility tests, higher cell adhesion and proliferation were found for the 60/40, 50/50 and 40/60 PCL/Ge compositions that was corroborated by MTT assay, fluorescence and microscopy. A weakened structure, more labile to the in vitro degradation in physiologic conditions was found for these compositions with higher dissolution times (72 and 96 h). Particularly, the 40/60 PCL/Ge scaffolds revealed an interesting progressive degradation behaviour as a function of the dissolution time. Moreover, these scaffolds were non-inflammatory, as revealed by the pyrogen test and after the 15-day subcutaneous in vivo implantation in mice. Finally, a reduction of the scar tissue area after infarction was found for the 40/60 PCL/Ge scaffolds electrospun after 72 h implanted in rat hearts. These results are especially interesting and represent a feasible way to avoid undesired inflammatory reactions during the scaffold assimilation.

Reprocessed polylactide: studies of thermo-oxidative decomposition.

The combustion process of virgin and reprocessed polylactide (PLA) was simulated by multi-rate linear non-isothermal thermogravimetric experiments under O(2). A complete methodology that accounted on the thermal stability and emission of gases was thoroughly developed. A new model, Thermal Decomposition Behavior, and novel parameters, the Zero-Decomposition Temperatures, were used to test the thermal stability of the materials under any linear heating rate. The release of gases was monitored by Evolved Gas Analysis with in-line FT-IR analysis. In addition, a kinetic analysis methodology that accounted for variable activation parameters showed that the decomposition process could be driven by the formation of bubbles in the melt. It was found that the combustion technologies for virgin PLA could be transferred for the energetic valorization of its recyclates. Combustion was pointed out as appropriate for the energetic valorization of PLA submitted to more than three successive reprocessing cycles.

A methodology to assess the energetic valorization of bio-based polymers from the packaging industry: pyrolysis of reprocessed polylactide.

The energetic valorization process of bio-based polymers is addressed in this study, taking polylactide (PLA) as model. The pyrolysis of virgin and multiple-injected PLA was simulated by means of multi-rate linear-non-isothermal thermogravimetric experiments. A complete methodology, involving control of gases, thermal stability and thermal decomposition kinetics was proposed. The release of gases was monitored by Evolved Gas Analysis of the fumes of pyrolysis, by in-line FT-IR, with the aid of 2D-correlation IR characterization. A novel model to establish the thermal stability of PLAs under any linear heating profile was proposed. A kinetic strategy was methodically applied to assess the thermal decomposition in terms of activation energy and kinetic model. It was found that the pyrolysis technologies for virgin PLA could be straightforwardly transferred for the valorization of its recyclates.

A statistical design of experiments for optimizing the MALDI-TOF-MS sample preparation of polymers. An application in the assessment of the thermo-mechanical degradation mechanisms of poly (ethylene terephthalate).

The sample preparation procedure for MALDI-TOF MS of polymers is addressed in this study by the application of a statistical Design of Experiments (DoE). Industrial poly (ethylene terephthalate) (PET) was chosen as model polymer. Different experimental settings (levels) for matrixes, analyte/matrix proportions and concentrations of cationization agent were considered. The quality parameters used for the analysis were signal-to-noise ratio and resolution. A closer inspection of the statistical results provided the study not only with the best combination of factors for the MALDI sample preparation, but also with a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measure of PET stated that the best combination of factors and levels was the following: matrix (dithranol), proportion analyte/matrix/cationization agent (1/15/1, V/V/V), and concentration of cationization agent (2 g L(-1)). In a second part, multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PET under mechanical recycling. The application of MALDI-TOF-MS showed that thermo-mechanical degradation primarily affected initially predominant cyclic species. Several degradation mechanisms were proposed, remarking intramolecular transesterification and hydrolysis. The ether links of the glycol unit in PET were shown to act as potential reaction sites, driving the main reactions of degradation.