Examinando por Autor "Lucio, B."

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Restringido
Catalytic effects over formation of functional thermoplastic elastomers for rocket propellants
(Wiley, 2021-11-22) Lucio, B.; De la Fuente, J. L.; Ministerio de Ciencia e Innovación (MICINN); Instituto Nacional de Técnica Aeroespacial (INTA); Gobierno Vasco
Rheometry was the main method to characterize the curing process of binders made of functional polyurethanes (PUs). The macroglycols characterization by means of additional techniques such as nuclear magnetic resonance, size exclusion chromatography and differential scanning calorimetry, provided further information for the chemorheological description. Materials were based on Butacene ((ferrocenylbutyl)dimethylsilane grafted to hydroxyl-terminated polybutadiene (HTPB)), used in the solid propulsion field. First, the flow parameters for the uncured reactive mixtures of Butacene and four different diisocyanates were analysed via viscometry and these were markedly influenced by the chemical structure of the curing agents. Analysing the rheokinetic constant values of the pre-gel stage for Butacene- and HTPB-reactive systems, relevant catalysis caused by the ferrocene moiety was detected when aliphatic reactants were used, such as isophorone diisocyanate or 1,6-hexamethylene diisocyanate (IPDI and HMDI, respectively). No catalytic effect was found for 2,4-toluene diisocyanate (2,4-TDI) or even for 4,4’-methylenediphenyl diisocyanate (4,4’-MDI). Finally, the use of dynamic rheology was useful to evaluate the critical points during gelation process, where the reactivity of curing agents was associated with the achievement of elastic properties. Both techniques agreed the reactivity order of curing agents with Butacene, which is 4,4’-MDI > HMDI >> 2,4-TDI ≥ IPDI. The knowledge of the structure-reactivity relationship and, moreover, the kinetics of the urethane network formation for these metallo-PUs is paramount in manufacturing processes for advanced thermoplastic elastomer applications.
Restringido
Chemorheology and Kinetics of High-Performance Polyurethane Binders Based on HMDI
(Wiley Online Library, 2021-01-21) Lucio, B.; De la Fuente, J. L.; Agencia Estatal de Investigación (AEI); Gobierno Vasco
Aliphatic diisocyanates, such as 1,6-hexamethylene diisocyanate (HMDI), are preferred curing agents for the formation of polyurethanes (PUs) in applications where resistance to abrasion or degradation by ultraviolet light takes precedence. Aside from the final properties, the curing agent plays a key role in the bulk manufacturing of such materials, and it mainly affects the polymerization kinetics and their rheology. The copolymerization of HMDI and a metallo-prepolymer derivative from hydroxyl-terminated polybutadiene (HTPB) is studied under isothermal conditions (50–80 °C). This study is carried out by means of an indirect method, using both rotational viscometry and dynamic rheometry. At the beginning of the process, the viscosity growth fit well to a first-order kinetic model. Afterward, the reactive system passes through gelation, from which only rheology is allowed for the investigation of the entire polymerization process. This transition is analyzed in depth together with predictions from percolation theory. The conversion degree is determined from rheological measurements, and then an autocatalytic kinetic model is applied to describe the overall process. Finally, an isoconversional method allows the evolution of activation energy to be studied. This analysis merits attention for the development of high-performance binders that are of great interest in aerospace propulsion technology.
Restringido
Kinetic and chemorheological modelling of the polymerization of 2,4- Toluenediisocyanate and ferrocene-functionalized hydroxyl-terminated polybutadiene
(Elsevier, 2018-02-26) Lucio, B.; De la Fuente, J. L.; Ministerio de Economía y Competitividad (MINECO)
The reaction of 2,4-toluenediisocyanate (2,4-TDI) and a metallocenic-prepolymer derived from hydroxyl-terminated polybutadiene (HTPB) was studied in bulk and under isothermal conditions (50–80 °C) by rheological methods. Two regions distinguished and limited by the gel point, identified as the crossover of loss tangent (tan δ) at different frequencies, were analysed from different rheological properties during the curing process of this novel metallo-polyurethane (PU). The initial part of this polymerization, dominated by the viscous behaviour (from η0 ≈ 5 Pa s to η = 250 Pa s), was modelled through the Arrhenius isothermal model, in which the presence of two rheokinetic stages, due to different isocyanate groups in the 2 and 4 positions for this asymmetric monomer, was found until the gelation is reached. The contributions of the main reactions for the region analysed, before the gel point of this polyaddition, are discussed. The gel transition was identified, and the viscoelastic behaviour of the gelation process was studied in depth. In addition, from the evolution of the storage modulus (G′) recorded, the overall polymerization reaction was described by a Kamal-Sourour kinetic expression for the reaction rate. The different kinetic parameters obtained for the autocatalytic model used yielded predictions that agree very well with the experimental data, finding a significant autocatalytic effect. An isoconversional method allowed the determination of the dependence of the activation energy on the conversion degree during the network formation of this advanced functional ferrocene-PU, which is of great interest in rocket technology research for the development of the aerospace industry.
Restringido
Rheological kinetics of ferrocenylsilane functionalized polyurethanes based on 4,4'-methylenediphenyl diisocyanate for advanced energetic materials
(Wiley, 2021-10-18) Lucio, B.; De la Fuente, J. L.; Ministerio de Ciencia e Innovación (MICINN); Gobierno Vasco
4,4’-Methylenediphenyl diisocyanate (4,4’-MDI) is a symmetric aromatic isocyanate commonly used as a curing agent in the production of polyurethanes (PUs). The chemorheology and kinetics of its reaction with a metallocenic-prepolymer derivative from hydroxyl-terminated polybutadiene (HTPB) is studied in bulk and under isothermal conditions at 50-80 °C by means of rheological measurements. The viscosity of the initial part of the PU formation, the pre-gel stage governed by viscous behaviour, is modelled through the Arrhenius rheokinetic model. This thermoplastic elastomer undergoes gelation, a transition that is analysed in depth together with predictions according to percolation theory. The gel point (tgel) is determined from the intersection in tan δ versus curing time for different shear frequencies. From the viscoelastic properties, like the elastic storage modulus (G´), the conversion degree is determined, and the entire polymerization process is modelled through the Kamal-Sourour and Sato kinetic expressions. Significant variation in the reaction orders and the activation energies might reveal a change in the process mechanism, depending on the temperature. This work demonstrates that an indirect method makes it possible to gain relevant knowledge about the chemistry of these thermoplastic PUs during curing, which is essential for their manufacturing. This study merits attention for the development of a new generation of high-performance binders with great potential in aerospace propulsion.