The role of activator and deactivator species in the surface‐initiated atom‐transfer radical polymerization of styrene using CuBr/CuBr2/pentamethyldiethylenetriamine as a model system is described. The influence of initially added deactivator with respect to the degree of controlling the layer growth and thickness is studied. Variation of the activator concentration results in changes of the kinetics as well as brush thicknesses consistent with the well‐known rate laws of ATRP.
We describe a simple photochemical process which allows fluoropolymers to be chemically bound at room temperature onto SiO2 surfaces. To achieve this, at first a benzophenone silane is used to form a self-assembled monolayer on the surface of the substrate, which is subsequently coated with the fluoropolymer and irradiated with UV light of wavelength 365 nm. Using this very simple approach, we have been able to create ultrahydrophobic surfaces with very low surface free energies together with a good degree of control in thickness and composition as well as strong adhesion to the monolayer. The use of a UV-based process to attach the films on SiO2 surfaces opens the door for photopatterning of surfaces with fluorinated and nonfluorinated compounds to yield well-defined microstructures with spatial control of the wetting properties of the substrates.
Nanoparticles used in adhesive resins are prone to agglomeration, turning the material susceptible to physical failure. Quantum dots are nonagglomerated inorganic nanoparticles (1 to 10 nm) when in equilibrium. The aim of the present study was to synthesize and characterize zinc oxide quantum dots (ZnO) and to develop and evaluate an adhesive resin with the addition of ZnO. ZnO were formulated by self-organization in chemical reaction with isopropanol and added to 2-hydroxyethyl methacrylate (HEMA). HEMA containing ZnO was used for the experimental group and neat HEMA for the control group. Mean ZnO diameter was evaluated in isopropanol and in HEMA by ultraviolet-visible spectroscopy. The adhesives were evaluated for degree of conversion ( n = 5), softening in solvent ( n = 5), ultimate tensile strength ( n = 5), microtensile bond strength ( n = 20) at 24 h and after 6 mo, SEM-EDS (scanning electron microscopy-energy-dispersive x-ray spectroscopy; n = 3), and superresolution confocal microscopy ( n = 3). Data of microtensile bond strength after 6 mo and Knoop hardness after solvent immersion were evaluated by paired t test with a 0.05 level of significance. The other data were evaluated by independent t test with a 0.05 level of significance. Ultraviolet-visible spectroscopy indicated that the mean ZnOQD diameter remained stable in isopropanol and in HEMA (1.19 to 1.24 nm). Fourier transform infrared spectroscopy analysis showed the peak corresponding to zinc and oxygen bond (440 cm). The experimental group achieved a higher degree of conversion as compared with the control group and presented dentin/adhesive interface stability after 6 mo without altering other properties tested. SEM-EDS indicated 1.54 ± 0.46 wt% of zinc, and the superresolution confocal microscopy indicated nonagglomerated nanoparticles with fluorescence blinking in the polymerized adhesive. The findings of this study showed a possible and reliable method to formulate composites with nonagglomerated nanoscale fillers, shedding light on the nanoparticle agglomeration concern.
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