Monitoring of the shrinkage during the photopolymerization of acrylates using hyphenated photorheometry/near‐infrared spectroscopy

This article describes a new method for the quantitative determination and time‐resolved monitoring of the polymerization shrinkage during ultraviolet (UV) photopolymerization. It is based on rheometry using a modified oscillating rheometer. Shrinkage is determined from the decrease of the gap between the rheometer plates. Moreover, near‐infrared (NIR) spectra can be recorded directly in the rheometer, which allows continuous determination of the conversion at any time of a shrinkage measurement. As both shrinkage and conversion data come from the same experiment, shrinkage can be analyzed in dependence on the current conversion achieved during UV irradiation, which enables direct investigation of correlations between both parameters. Hyphenated photorheometry/FT‐NIR spectroscopy was used for the determination of the polymerization shrinkage of pure acrylate monomers and oligomers as well as acrylate‐based formulations. Quantitative shrinkage values were found to be in excellent correlation with data that were determined by an independent method (via buoyancy measurements) and data from literature. Furthermore, the effect of ambient and irradiation conditions or the content of nanoparticles on the degree of shrinkage was studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 729–739     

Shape-Aware Matching of Implicit Surfaces Based on Thin Shell Energies

A shape sensitive, variational approach for the matching of surfaces considered as thin elastic shells is investigated. The elasticity functional to be minimized takes into account two different types of nonlinear energies: a membrane energy measuring the rate of tangential distortion when deforming the reference shell into the template shell, and a bending energy measuring the bending under the deformation in terms of the change of the shape operators from the undeformed into the deformed configuration. The variational method applies to surfaces described as level sets. It is mathematically well-posed, and an existence proof of an optimal matching deformation is given. The variational model is implemented using a finite element discretization combined with a narrow band approach on an efficient hierarchical grid structure. For the optimization, a regularized nonlinear conjugate gradient scheme and a cascadic multilevel strategy are used. The features of the proposed approach are studied for synthetic test cases and a collection of geometry processing examples.     

The thermal and initiated thermal decomposition of biacetyl-d6

The thermal and methyl radical initiated decomposition of biacetyl-d₆ were investigated at conversions 5% over the temperature range of 387-412°C and 251–292°C, respectively. The deuterated sample contained 10.5% biacetyl-d₅. The reaction products were analyzed by mass spectrometry. The following data could be determined from product ratios: where E is in kcal/mol With reasonable assumptions and literature data Arrhenius parameters for elementary steps were derived and discussed in particular with respect to isotopic effects in H/D-abstraction reactions.     

Experiments,modelling and simulation of adhesive curing processes in bonded three dimensional curved piezo metal composite structures

This contribution deals with the modelling and simulation of curing phenomena in adhesively bonded piezo metal composites which consists of a piezoelectric module enclosed by an adhesive layer which in turn is surrounded by two metal sheets. A short survey on the neccessary experimental investigations to characterise the adhesive's material behaviour is given and important aspects on the corresponding phenomenological modelling approach are presented. Both steps take into account the curing reaction, changes of volume, like chemical shrinkage, and inelastic mechanical behaviour which is temperature and curing dependent. Finally, the simulation strategy for the modelling within a finite element environment is depicted. By this, residual stresses, secondary deformations and loads on the piezo modules can be predicted, which is exemplified by a comparative study verifying a novel manufacturing strategy. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The sputtering mechanism for low-energy light ions

The computer simulation program MARLOWE which follows the trajectories of energetic ions and recoiling target atoms in solids has been used to calculate sputtering yields for low energy (0.1–10keV) light ions (H, D, T,⁴He). Recoil energy densities were calculated for comparison with analytical theories. The sputtering yields obtained for amorphous Fe agree within a factor of two with experimentally measured values for polycrystalline stainless steel, while the calculated yields for protons on amorphous molybdenum are more than twice the experimental values on polycrystalline material. The calculations show that in the parameter range investigated, ions backscattered in the solid contribute a major part to sputtering. This result confirms earlier calculations of the threshold energy for sputtering which are in agreement with recent measurements. Operated for the United States Department of Energy by the Union Carbide Corporation.