317 research outputs found

    Latent curing of epoxy-thiol thermosets

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    Epoxy-thiol curing is a click reaction which allows quantitative yield of the end products. The base-catalyzed reaction is rapid at low temperatures so it is most often desirable to harness reactivity by using latent catalysts. In this work, we used triazabicyclodecene tetraphenylborate (TBD¡HBPh4) as a photobase generator (PB). We activated the PB either thermally or by UV light and monitored reaction kinetics by DSC and FTIR methods. Depending on the catalytic system used, the rate of the thiol-epoxy reaction was ordered as follows: Neat base > UV activated PB > thermally activated PB > uncatalyzed system. A series of isothermal and non-isothermal DSC experiments were run on non-irradiated and irradiated samples in order to study the effect of PB content and UV irradiation duration on PB activation efficiency and latency/storage stability. The data from DSC were analyzed using model-free linear isoconversional methods to estimate kinetic parameters such as activation energies. In addition, the kinetics data for both activation methods were shown to be accurately represented by multi-term Kamal models. The storage stability of the systems were studied at room temperature and was shown to fit well to the predictions of the kinetic model.Postprint (author's final draft

    Sequential curing of amine-acrylate-methacrylate mixtures based on selective aza-Michael addition followed by radical photopolymerization

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    Dual curing systems find various uses in industry with the process flexibility they provide which allows tailoring properties at different curing stages in accordance with application requirements. A safe and efficient dual curing scheme is proposed here for a set of mixtures containing different proportions of acrylates and methacrylates. The first curing stage is a stoichiometric aza-Michael addition between acrylates and an amine, followed by photo-initiated radical homopolymerization of methacrylates and remaining acrylates. An analysis of aza-Michael reaction kinetics confirmed that amines react selectively with acrylates, leaving methacrylates unreacted after the first curing stage. It was found that acrylate-rich mixtures achieve complete global conversion at the end of the scheme. However, the highest crosslinking density and thermal resistance was observed in a methacrylate-rich formulation. The resulting materials show a wide range of viscoelastic properties at both curing stages that can be tailored to a variety of industrial application needs.Postprint (author's final draft

    L'art possible de la memòria

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    Acetoacetate based thermosets prepared by dual-Michael addition reactions

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    A novel set of dual-curable multiacetoacetate-multiacrylate-divinyl sulfone ternary materials with versatile and manipulable properties are presented. In contrast to common dual-curing systems, the first stage polymer herein consists of a densely crosslinked, high Tg network as a result of base-catalyzed multiacetoacetate-divinyl sulfone Michael addition. A more flexible secondary network forms after base-catalyzed Michael addition of remaining multiacetoacetate to multiacrylate. Curing is truly sequential as the rates of the two Michael additions are significantly different. Curing kinetics were analyzed using differential scanning calorimetry (DSC) and Fourier-transform infrared (FTIR). The materials at each curing stage were characterized using dynamic mechanical analysis (DMA) and SEM. Although some phase separation was observed in certain formulations, the incompatibilities were minimized when the molar percentage of the acetoacetate-divinyl sulfone polymer network was above 75%. Furthermore, the environmental scanning electron microscopy (ESEM) images of these materials show that the more flexible acetoacetate-acrylate phase is dispersed in the form of polymeric spheres within the rigid acetoacetate-divinyl sulfone matrix. This unique dual microstructure can potentially render these materials highly resilient in applications requiring densely crosslinked polymer architectures with enhanced toughnesPostprint (published version

    Characterization of sex, age, and breed for a population of canine leishmaniosis diseased dogs.

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    Our study of a large canine population investigated whether the development of symptomatic canine leishmaniosis revealed any predilection for sex, age, or breed. Included in the study were 390 leishmaniosis-affected dogs that had been treated at the Hospital Clínic Veterinari attached to the Universitat Autònoma de Barcelona. Of the diseased dogs, 238 were male (61%) and 152 were females (39%), whereas percentages for males and females in the overall reference population of dogs treated at this unit were 53% and 47%, respectively, (P<0.05). Age distribution was bimodal, with the highest prevalence of the disease occurring at 2-4 years of age and a secondary peak occurring at seven years or over. The over represented breeds were the German shepherd (13.6% versus 6.35%, P<0.001), the Rottweiler (13.1% versus 3.0%, P<0.001), and the Boxer (7.9% versus 4.7%, P=0.002), whereas the underrepresented breeds were the Yorkshire terrier (0.5% versus 6.5%, P<0.001), and the Poodle (0.3% versus 3.0%, P<0.001)

    Sequential heat release: an innovative approach for the control of curing profiles during composite processing based on dual-curing systems

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    The sequential heat release (SHR) taking place in dual-curing systems can facilitate thermal management and control of conversion and temperature gradients during processing of thick composite parts, hence reducing the appearance of internal stresses that compromise the quality of processed parts. This concept is demonstrated in this work by means of numerical simulation of conversion and temperature profiles during processing of an off-stoichiometric thiol–epoxy dual-curable system. The simulated processing scenario is the curing stage during resin transfer moulding processing (i.e. after injection or infusion), assuming one-dimensional heat transfer across the thickness of the composite part. The kinetics of both polymerization stages of the dual-curing system and thermophysical properties needed for the simulations have been determined using thermal analysis techniques and suitable phenomenological models. The simulations show that SHR makes it possible to reach a stable and uniform intermediate material after completion of the first polymerization process, and enables a better control of the subsequent crosslinking taking place during the second polymerization process due to the lower remaining exothermicity. A simple optimization of curing cycles for composite parts of different thickness has been performed on the basis of quality–time criteria, producing results that are very close to the Pareto-optimal front obtained by genetic algorithm optimization procedures.Postprint (author's final draft

    Mechanical characterization of sol–gel epoxy-silylatedhyperbranched poly(ethyleneimine) coatings by meansof Depth Sensing Indentation methods

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    A series of hybrid epoxy-silica coatings were prepared from a synthesized hyperbranched poly(ethyleneimine) with ethoxysilyl groups at the chain ends and diglycidylether of bisphenol A in different proportions. The curing procedure was based in a first sol-gel reaction performed at 80 °C in a humid chamber followed by the anionic homopolymerization of epoxides initiated by 1-methylimidazole in an oven at 180 °C. The prepared coatings were characterized mechanically by means of Depth Sensing Indentation technique. The influence of physical ageing on indentation hardness has been evaluated. The kinetic of the delayed depth recovery has been analyzed using the phenomenological so-called Kohlrausch-Williams-Watts relaxation function. It has been found that silylated hyperbranched poly(ethyleneimine) improves simultaneously the mechanical coating performance and the elastic recovery.Postprint (author's final draft

    Analysis of the reaction mechanism of the thiol-epoxy addition initiated by nucleophilic tertiary amines

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    A kinetic model for thiol–epoxy crosslinking initiated by tertiary amines has been proposed. The kinetic model is based on mechanistic considerations and it features the effect of the initiator, hydroxyl content, and thiol–epoxy ratios. The results of the kinetic model have been compared with data from the curing of off-stoichiometric formulations of diglycidyl ether of bisphenol A (DGEBA) crosslinked with trimethylolpropane tris(3-mercaptopropionate) (S3) using 1-methylimidazole (1MI) as the initiator. The model has been validated by fitting the kinetic parameters to the experimental data under a variety of reaction conditions. In spite of the experimental uncertainty and model assumptions, the main features of the curing kinetics are correctly described and the reaction rates are quantitatively reproduced.Postprint (published version

    Epoxy sol-gel hybrid thermosets

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    Sol-gel methodologies are advantageous in the preparation of hybrid materials in front of the conventional addition of nanoparticles, because of the fine dispersion of the inorganic phase that can be reached in epoxy matrices. In addition, the use of organoalkoxysilanes as coupling agents allows covalent linkage between organic and inorganic phases, which is the key point in the improvement of mechanical properties. The sol-gel process involves hydrolysis and condensation reactions under mild conditions, starting from hydrolysable metal alkoxides, generally alkoxy silanes. Using the sol-gel procedure, the viscosity of the formulation is maintained, which is an important issue in coating applications, whereas the transparency of the polymer matrix is also maintained. However, only the proper combination of the chemistries and functionalities of both organic and inorganic structures leads to thermosets with the desired characteristics. The adequate preparation of hybrid epoxy thermosets enables their improvement in characteristics such as mechanical properties ( modulus, hardness, scratch resistance), thermal and flame resistance, corrosion and antimicrobial protection, and even optical performance among others.Postprint (published version

    Structural design of CANs with fine-tunable relaxation properties: a theoretical framework based on network structure and kinetics modeling

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    In this work, we present a model capable of reproducing the stress relaxation dynamics of a wide range of relaxation processes in covalent adaptable networks (CANs) produced by stepwise polymerization. The proposed model captures the effective elastic response of the material subject to an initial stress by analogy with a network decrosslinking process. The combination of a recursive structural model and a kinetic model for the bond exchange reaction makes it possible to predict the expected stress relaxation profile in simple and complex systems depending on the structure of the network, the rate of bond exchange of the different components, and the presence of permanent bonds. After the basic features of the model are analyzed, its prediction capabilities are validated by simulating a number of scenarios taken from the literature. The results show that tailoring of the network architecture enables unprecedented flexibility in the design of CAN-based materials.This work was funded by the Spanish Ministry of Science and Innovation (MCIN/AEI/10.13039/501100011033) through R&D project PID2020-115102RB-C22 and also by Generalitat de Catalunya (2017-SGR-77). X. Fernåndez-Francos and O. Konuray acknowledge the Serra-Hunter ́ programme (Generalitat de Catalunya).Postprint (published version
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