Latent curing of epoxy-thiol thermosets

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

Dual and anti-dual modes in dielectric spheres

We present how the angular momentum of light can play an important role to induce a dual or anti-dual behaviour on a dielectric particle. Although the material the particle is made of is not dual, i.e. a dielectric does not interact with an electrical field in the same way as it does with a magnetic one, a spherical particle can behave as a dual system when the correct excitation beam is chosen. We study the conditions under which this induced dual or anti-dual behaviour can be induced.Comment: 13 pages, 5 figure

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

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

Acetoacetate based thermosets prepared by dual-Michael addition reactions

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

Price rivalry in airline markets: a study of a successful strategy of a network carrier against a low-cost carrier

Competition in airline markets may be tough. In this context, network carriers have two alternative strategies to compete with low-cost carriers. First, they may establish a low-cost subsidiary. Second, they may try to reduce costs using the main brand. This paper examines a successful strategy of the first type implemented by Iberia in the Spanish domestic market. Our analysis of data and the estimation of a pricing equation show that Iberia has been able to charge lower prices than rivals with its low-cost subsidiary. The pricing policy of the Spanish network carrier has been particularly aggressive in less dense routes and shorter routes.Airlines, competition, low-cost carriers JEL classification:L13, L59, L71

Near real time seismic data from the coastal ocean

A moored-buoy system for collecting near real-time seismic data from the coastal ocean has been developed and will be deployed for its initial field trial in the fall of 2016. The technology that makes possible the near real time telemetry of seismic data is the inductive modem technology. This type of data telemetry provides a solution that is convenient, economical, reliable, and flexible. We present results of a prototype system that demonstrate the feasibility of this concept. It will transmit continuous data at a rate of about 1000 bps to a radio link in the surface buoy. A GPS receiver on the surface buoy will be configured to perform accurate and synchronized timestamps on the seismic data on the sea surface, which will make it possible to include data from these undersea systems in the existing seismic data network. Power to operate the system will be supplied by solar panels and rechargeable batteries on the surface buoy and batteries on OBS.Peer ReviewedPostprint (published version

Isotropically polarized speckle patterns

The polarization of the light scattered by an optically dense, random solution of dielectric nanoparticles shows peculiar properties when the scatterers exhibit strong electric and magnetic polarizabilities. While the distribution of the scattering intensity in these systems shows the typical irregular speckle patterns, the helicity of the incident light can be fully conserved when the electric and magnetic polarizabilities of the scatterers are equal. We show that the multiple scattering of helical beams by a random dispersion of "dual" dipolar nano-spheres leads to a speckle pattern exhibiting a perfect isotropic constant polarization, a situation that could be useful in coherent control of light as well as in lasing in random media.Comment: 5 pages, 3 figure