Role of radicals in UV‐initiated postplasma grafting of poly‐ε‐caprolactone: An electron paramagnetic resonance study

Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The Gibbs' phenomenon

This paper analyses the answers of a group of first-year university Mathematics students to a questionnaire, with the aim of determining the difficulties they have when carrying out non-routine tasks related to improper integrals. The questionnaire consisted of nine questions including not only calculus tasks and determining the convergence of given improper integrals, but also intuitive questions and some paradoxical results too (for example, a figure with an infinite longitude which closes the same area as the unit circumference, or an infinite figure with a finite volume). In particular, the students were asked to interpret most of the results they had obtained. Answers given by the students to each of the questions were categorized, which allowed some initial conclusions to be reached regarding this research. From analyses carried out, one can conclude that there are students who have difficulties in articulating the different systems of representation, and have problems in connecting and relating this knowledge as a generalization of previous concepts, such as definite integrals, series and sequences.     

Convexity preserving C 0 splines

Linear conditions for a C ⁰ spline to be convex are developed and used to create some convexity preserving interpolation and approximation methods.     

Heat capacity of the white pine biocarbon preform and the related biocarbon/copper composite

This paper reports on measurements in the 80–300-K temperature interval of the heat capacity at constant pressure C _p (T) of high-porosity amorphous white pine carbon preforms (biocarbon) prepared by pyrolysis (carbonization) at T _carb = 1000 and 2400°C in an argon flow. The dependences C _p (T) for biocarbon/copper composites based on the carbon preforms obtained have also been determined. It is shown that the mixture rule holds for the composites, i.e., that C _p (T) of the composite is a sum of the heat capacities of the constituent materials taken in the corresponding ratios. Phonon mean free paths for the white pine carbon preforms prepared at T _carb = 1000 and 2400°C have been calculated and used to estimate the size of the nanocrystallites contributing to formation of the carbon frameworks of these preforms.