Synthesis of gold and silver hydrosols was carried out in a one-step process by reduction of aqueous solutions of metal salts using poly(N-vinyl-2-pyrrolidone) (PVP). Both kinds of metal nanoparticles were obtained without the addition of any other reducing agent, at low temperatures and using water as the synthesis solvent. Shape, size, and optical properties of the particles could be tuned by changing the employed PVP/metal salt ratio. It is proposed that PVP acts as the reducing agent suffering a partial degradation during the nanoparticles synthesis. Two possible mechanisms are proposed to explain the reduction step: direct hydrogen abstraction induced by the metal ion and/or reducing action of macroradicals formed during degradation of the polymer. Initial formation of the macroradicals might be associated with the metal-accelerated decomposition of low amounts of peroxides present in the commercial polymer.
Superparamagnetic nanocomposites were obtained by dispersion of oleic acid (OA)-coated magnetite NPs in an epoxy system based on diglycidylether of bisphenol A (DGEBA) modified with OA. Dispersion of conventional oleic acidstabilized magnetite NPs in a typical epoxy matrix is not possible due to the dissimilar chemical structures of the organic coating and the reactive solvent. However, by modification of a DGEBA-based epoxy with 20 wt % OA, we obtained a suitable reactive solvent to disperse up to at least 8 wt % of OA-stabilized magnetite NPs. A tertiary amine was used to catalyze the epoxy−acid reaction and initiate the homopolymerization of the epoxy excess. Both reactions occurred practically in series, first the epoxy−acid and then the epoxy homopolymerization. It was necessary to complete the first reaction to attain a very good dispersion of magnetite NPs in the reactive solvent previous to the occurrence of the final reaction. Magnetization curves and TEM images revealed a uniform dispersion of individual nanoparticles in the cross-linked epoxy. A sample containing 8 wt % OA-coated magnetite NPs exhibited a temperature increase of 25 °C at its surface when exposed to an alternating magnetic field. The temperature increase was enough to induce the shape memory effect of the nanocomposite.
Vitrimers are covalently crosslinked polymers that behave as conventional thermosets below the glass transition temperature (T g ) but can flow above a particular temperature, T v > T g , by bond exchange reactions. In epoxy vitrimers, transesterification reactions are responsible for their behavior at T > T v that enables flow, thermoforming, recycling, self-healing and stress relaxation. A statistical analysis based on the fragment approach was performed to analyze the evolution of the network structure of epoxy vitrimers during transesterification reactions. An analytical solution was obtained for a formulation based on a diepoxide and a dicarboxylic acid. A numerical solution was derived for the reaction of a diepoxide with a tricarboxylic acid, as an example of the way to apply the model to polyfunctional monomers. As transesterification acts as a disproportionation reaction that converts two linear fragments (monoesters) into a terminal fragment (glycol) and a branching fragment (diester), its effect on network structure is to increase the concentration of crosslinks and pendant chains while leaving a sol fraction. Changes in the network structure of the epoxy vitrimer can take place after their synthesis, during their use at high temperatures, a fact that has to be considered in their technological applications.
Polymer-dispersed liquid crystals (PDLCs), consisting of a dispersion of LC-rich domains
in a polymer matrix, are used in different types of electrooptical devices. Their efficiency can in principle
be increased if the LC domains exhibit a uniform characteristic size in the range of the wavelength of
visible light. In an attempt to generate this type of morphology, a model PDLC system based on a 50 wt
% solution of N-4-ethoxybenzylidene-4‘-n-butylaniline (EBBA) in an epoxy monomer (diglycidyl ether of
bisphenol A, DGEBA) was analyzed. The polymerization-induced phase separation was performed at 80
°C, using a tertiary amine as initiator (benzyldimethylamine, BDMA). By selecting an initial concentration
located close to the critical composition to promote spinodal demixing, co-continuous morphologies were
obtained, which were rapidly fixed by gelation. The conversion of epoxy groups (p) was followed by near-infrared spectroscopy (NIR). At p = 0.28, phase separation took place as revealed by transmission optical
microscopy (TOM) and by the acceleration observed in the isothermal cure rate. Gelation took place at p
= 0.35, soon after the cloud point. Although the primary structure was arrested by gelation, the LC-rich
phase was continuously enriched in pure EBBA, as revealed by the increase in T
NI with conversion
monitored by differential scanning calorimetry (DSC). Co-continuous structures remained unmodified
after the storage of PDLCs for several months. The nematic range of the LC-rich phase at p = 1 was
comprised between 34 °C (melting point) and T
NI = 68 °C. A 57% of the initial LC was present in nematic
domains at 40 °C, as determined by the variation of the FTIR absorbance of a characteristic LC peak
between isotropic and nematic states. Therefore, a possible route to obtain PDLCs with a uniform
characteristic size of LC domains is to start with a composition close to the critical one and select conditions
to produce liquid−liquid demixing soon before gelation.
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