Photochemical grafting of acrylated azo dyes onto polymeric surfaces. VII. Kinetics and mechanism of dye-sensitized photoinitiation of some diacrylates

Photoinitiated grafting and graft polymerization of liquid mixtures, adsorbed onto polypropylene, polycaprolactam, and poly(ethylene terephthalate) films, containing one of four acryloxy-substituted aromatic diazenes and one of four diacrylate comonomers, in the presence of 1,2-diphenyl-2,2-dimethoxyethanone as photoinitiator, were investigated kinetically at 30 ± 2°C. Irradiation was carried out polychromatically, with impinging photoenergy from 2.1 × 10^?8 to 20.5 × 10^?8 einstein s^?1 cm^?2; in some of the runs the ultraviolet radiation was filtered. The ratio R between the molar concentration of photoinitiator and the sum of concentrations of dye and diacrylate varied between 0.005 and 0.095; the ratio M between the molar concentration of dye and diacrylate varied between 0.005 and 0.046. The moles of dye and diacrylate n initially deposited per unit apparent polymeric surface S varied between 2 and 74 μmol cm^?2. No selective effect was shown by the presence of dyes in the comonomer mixture. The surface density of grafted molecules at the end of the grafting process was not affected by the photoinitiator concentration (for 0.030 < R < 0.095), by diacrylate or dye concentrations, or by the kind of polymer substrate. This parameter, on the contrary, clearly depended on n/S, and linearly up to n/S ? 30 μmol cm^?2. Quantum efficiencies for the two consecutive kinetic processes of grafting and graft polymerization (Φ₁ and Φ₂, respectively) were evaluated. The dependency of Φ₁ on R, as well as of Φ₂ on n/S, are critically discussed on the basis of the proposed mechanism involving grafting of an oligomeric chain (Φ₁ values up to the order of 10²) followed by a step-by-step graft polymerization (Φ₂ limiting values of the order of unity). The sensitizing effect of acryloxy-substituted aromatic diazenes on both Φ₁ and Φ₂ is evidenced.     

Development and evaluation of a virtual campus on Second Life: The case of SecondDMI

Video games and new communication metaphors are quickly changing today’s young people habits. Considering the actual e-learning scenarios, embedded in a fully technological enabled environment it is crucial to take advantage of this kind of capabilities to let learning process gain best results.     

Nanocomposite epoxy coatings containing rare earth ion-doped LaF3 nanoparticles: Film preparation and characterization

New epoxy-based nanostructured materials containing lanthanide ions doped LaF₃ nanoparticles were obtained by cationic UV-induced ring-opening polymerization.The lanthanide Er³⁺ and Yb³⁺ ions were added as dopant to LaF₃ nanoparticles. The synthesized NPs were solubilized into cyclohexene oxide and afterwards dispersed, in the range between 3 and 20 wt.%, into CE as dicycloaliphatic epoxy resin. The cured films were completely transparent and TEM analysis showed the absence of macroscopic agglomeration. The fast UV curing process was shown to be efficient on “freezing” the good nanometric dispersion achieved in the liquid formulations. These new materials could find suitable applications in optical communication and in LASER waveguide direct writing.     

Mechanically Induced Phase Transformation and Surface Segregation in Bismuth-Doped Tetragonal Zirconia

Compact pressure causes a martensitic transformation of partially stabilized tetragonal bismuth-doped ZrO₂ powders to the monoclinic phase. A similar effect is not observed when pelletization, followed by firing, of amorphous bismuth/ZrO₂ is performed. The stress-induced transition has been monitored via X-ray diffractometry, Raman spectroscopy, and Fourier transform infrared reflectivity. Surface bismuth segregation, which involves few ionic planes, has been probed by angle-resolved X-ray photoelectron spectroscopy. The bismuth segregation enthalpy has been evaluated.     

Photosynthetic membranes, 21. Immobilization of catalase by photochemically grafted ultrafiltration membranes

Catalase has been immobilized in membranes prepared by photoinduced grafting onto microporous polymeric supports and its catalytic activity on hydrogen peroxide decomposition has been studied under ultrafiltration conditions by means of a recirculation apparatus. The membranes showed a very good catalytic performance and the enzyme reaction took place exclusively within the membrane structure. Initial reaction rates measured in the temperature range 5 – 35°C as a function of both substrate concentration and enzyme amount immobilized per unit membrane surface indicate that the mechanism of action of catalase is not altered after immobilization.     

A model study for release of plasticizers from polymer films through vapor phase

A model has been applied to release of plasticizers from polymer films through vapor phase, for which the overall rate of release may be generally determined by evaporation of the plasticizer from the surface of the film, and/or by migration to the surface at below saturation in the polymer. The experimental system employed made use of n-butyl formate, diethyl-phthalate, di-n-butylphthalate, and N,n-butylbenzenesulfonamide as model molecules in polycaprolactam films, both with the aims of studying undesirable loss of plasticizers, and of simulating a model able to envisage releasing, at a constant rate, of any desired additive, with relatively high solubility and vapor pressure, to the content of packaging films. Experimental measurements were made (at 298–333 K) by investigating in a suitable cell the permeation of plasticizers both at concentrations below and above the saturation limit. Rate of evaporation of plasticizers from the membrane surface above the saturation limit, measured in this cell, were found to coincide satisfactorily with those calculated by application of the mass transfer theory to evaporation from a stationary liquid into a stirred gas, at a known velocity of gas flowing past the surface. From these latter rates and solubilities, the mass transfer coefficients H for evaporation could be obtained, as well as from experimental time lags the diffusivities D_p through the polymer membrane. In the light of the theoretical model a correlation was found between activation energies of H and evaporation enthalpies of the model molecules.     

Photochemical grafting of acrylated azo dyes onto polymeric surfaces,IV. Grafting of 4-(N-ethyl-N-2-acryloxyethyl)amino-4′-nitro-azobenzene onto cellulose

Photochemically induced grafting and graft-polymerization of 4-(N-ethyl-N-2-acryloxyethyl)amino-4′-nitro-azobenzene I , brought into contact in the solid state with cellulose by evaporation of solvent from monomer solutions, has been investigated kinetically at 30°C. Two constant rate periods were observed. The first one was interpreted on the basis of a self-sensitized grafting mechanism of monomeric or oligomeric species of I , photochemically initiated by hydrogen abstraction from the cellulose surface. The second one was explained as a self-sensitized photochemically induced graft-polymerization of I on the first grafted layer. Some particular features, such as concurrent photodegradation of the first grafted layer at low surface coverage, are discussed in the light of the proposed mechanism.     

3D‐Printing of High‐κ Thiol‐Ene Resins with Spiro‐Orthoesters as Anti‐Shrinkage Additive

Tri(ethylene glycol) divinyl ether and the spiro‐orthoester 2‐((allyloxy)methy)‐1,4,6‐trioxospiro[4.4]nonane can be formulated in different ratios and crosslinked by thiol‐ene reactions. The spiro‐orthoester is used as anti‐shrinkage additive, enabling shrinkage reduction of up to 39%. Addition of a radical photoinitiator for the thiol‐ene reaction and a cationic photoinitiator for the double ring‐opening of the spiro‐orthoester enables dual‐curing for application in 3D‐printing. The formulation free of the spiro‐orthoester shows gelation during the printing process and, correspondingly, low resolution. The formulations containing the spiro‐orthoester exhibit higher resolutions in the range of 50 µm. The resins containing mixtures of tri(ethylene glycol) divinyl ether and the spiro‐orthoester show permittivities as high as 10⁴. The dielectric loss factor of the resins is in the range of 0.5–7.6, and the conductivity in the range of 1.3?10^?11 to 2.0?10^?11 S cm^?1. These high‐κ materials can be 3D‐printed by digital light processing for the next generation of electronic materials.