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- Suberin-based polyurethanes: synthesis, characterization and kinetics of their formationPublication . Cordeiro, N.; Belgacem, M. N.; Gandini, A.; Pascoal Neto, C.
- Fraccionamento da cortiça e caracterização dos seus componentes: estudo de possibilidades de valorização suberinaPublication . Cordeiro, Nereida Maria Abano
- Urethanes and polyurethanes from suberin 2: synthesis and characterizationPublication . Cordeiro, N.; Belgacem, M.N.; Gandini, A.; Pascoal Neto, C.Polyurethanes based on suberin from cork of Quercus suber L. and conventional isocyanate monomers were prepared and fully characterized in terms of both structure (FTIR and 1 H NMR spectroscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). Two fractions were systematically isolated, namely (i) methylene-chloride soluble products, which corresponded to linear and branched macromolecules and (ii) methylene-chloride insoluble products, representing the crosslinked material. The structures of these polymers were regular and no appreciable side reactions were detected. DSC analyses provided information about the glass transition temperature of both fractions and this parameter was correlated with the stiffness of the isocyanate used. The TGA of these polyurethanes showed that they started to degrade at about 175°C and that the residue at 400°C was around 50%. The highest amounts of insoluble fractions, as well as the highest Tgs, were reached when an initial [NCO]/[OH] of unity was used.
- Products of the permanganate oxidation of Cork, desuberized Cork, suberin and lignin from Quercus suber L.Publication . Lopes, M.; Neto, C. Pascoal; Evtuguin, D.; Silvestre, A. J. D.; Gil, A.; Cordeiro, N.; Gandini, A.
- Surface properties of suberinPublication . Cordeiro, Nereida; Aurenty, Patrice; Belgacem, Mohamed Naceur; Gandini, Alessandro; Neto, Carlos PascoalThe surface energy of suberin was determined by four different methods, namely, (i) contact angle measurements, (ii) Wilhelmy plate measurements, (iii) maximum bubble pressure, and (iv) inverse gas chromatography (IGC). The first three methods gave a gammasub value in the range 40-50 mN m-1 at room temperature. The major component of this value reflects the dispersive contribution. The IGC measurements showed a higher dispersive term, which is common with this method of characterization. The surface acid (A)/base (B) properties were also evaluated, and the results indicated that suberin has an acidic character.
- Cork suberin as a new source of chemicals.: 1. isolation and chemical characterization of its compositionPublication . Cordeiro, N.; Belgacem, M.N.; Silvestre, A.J.D.; Pascoal Neto, C.; Gandini, A.Extractive-free cork from Quercus suber L. was submitted to a solvolysis treatment with methanolic NaOH which yielded 37% (o.d. cork) of suberin. This mixture of compounds was thoroughly characterized by FTIR, 1 H- and 13C-NMR, gas chromatogra phy coupled with mass spectrometric (GC–MS) analysis, vapour pressure osmometry (VPO), mass spectrography (MS) and gel permeation chromatography (GPC). After derivatization, the main components of the volatile fraction, representing less than half of the total, were found to be v-hydroxymonocarboxylates, a,v-dicarboxylates, simple alkanoates and 1-alkanols, all with chain lengths ranging from C16 to C24. A second fraction, with an average molecular weight about three times higher, was detected by VPO, MS and GPC. The presence of this important fraction in cork suberin had not been recognized in earlier studies. Both fractions constitute interesting precursors for the elaboration of new materials.
- A discrete model for the design sensitivity analysis of multi-layered composite shells of revolutionPublication . Soares, Cristovão M. Mota; Cordeiro, N. M. Marques; Barbosa, J. InfanteThis paper studies the sensitivity analysis for the optimization of the multi-layered composite axisymmetric shells subjected to arbitrary static loading and free vibrations. The structural analysis is carried out using a two node frustum-cone finite element with 16 degrees of freedom based on Love-Kirchhoff assumptions. The design variables are the angle of orientation of the fibers and/or the vectorial distances from middle surface to upper surface of each ply. The constraint functions are displacements, stresses (Tsai-Hill criterion) and the natural frequency of a specified mode shape. Four types of objective functions can be used: maximum displacement or natural frequency or elastic strain energy and material volume. The design sensitivities are calculated analytically, semi-analytically and by global finite difference. The potentiality of the proposed model and the accuracy of the sensitivities of response are discussed with reference to the applications.
- Urethanes and polyurethanes from suberin: 1. Kinetic studyPublication . Cordeiro, Nereida; Belgacem, Mohamed Naceur; Gandini, Alessandro; Neto, Carlos PascoalWithin the context of a study on the preparation and the characterization of polyurethanes based on suberin, as a polyol, and conventional polyisocyanates, it was deemed necessary to carry out a preliminary study on the reactivity of the hydroxy functions of suberin. Aliphatic and aromatic mono- and di-isocyanates were tested and the kinetics of this system followed the classical second order up to conversions of about 85%. The influence of the steric hindrance and the electronic factors, linked to the specific structures of both types of isocyanates, was established.
- Cork suberin as a new source of chemicals: 2. crystallinity, thermal and rheological propertiesPublication . Cordeiro, N.; Belgacem, N.M.; Gandini, A.; Neto, C. PascoalSuberin samples, obtained by alkaline methanolysis from cork (Quercus suber L.), were submitted to various physical characterizations; DSC, TGA, optical microscopy, density and rheological properties. A sub stantial proportion of these oligomers possessed a microcrystalline character with a melting range between 0 and 50°C. The amorphous part was liquid at room temperature and did not display a detectable glass transition upon cooling because of its wide molecular weight distribution. The viscous behaviour of suberin at room temperature was both plastic and thixotropic because of the structuring role of the microcrystals.
- Characterization of the cork surface by inverse gas chromatographyPublication . Cordeiro, Nereida; Neto, Carlos Pascoal; Gandini, Alessandro; Belgacem, Mohamed NaceurInverse gas chromatography (IGC) at infinite dilution has been used to study the surface properties of cork from Quercus suber. The dispersive component of its surface energy was determined at different temperatures using n -alkanes as probes, and a γDS value of 38 ± 1 mJ · m-2 at 40°C was obtained. The surface acid (A)/base (B) properties were also evaluated by using polar probes and the results indicate that cork has an amphoteric character, with a KA /KB = 1.1. The advantages of IGC, compared with the technique of contact angle measurements in the characterization of the cork surface, are discussed.