The mutual diffusion coefficient for (meth)acrylate monomers as determined with a nuclear microprobe

The value of the mutual diffusion coefficient DV of two acrylic monomers is determined with nuclear microprobe measurements on a set of polymer films. These films have been prepared by allowing the monomers to diffuse into each other for a certain time and subsequently applying fast ultraviolet photo-polymerization, which freezes the concentration profile. The monomer diffusion profiles are studied with a scanning 2.1 MeV proton microprobe. Each monomer contains a marker element, e.g., Cl and Si, which are easily detected with proton induced x-ray emission. From the diffusion profiles, it is possible to determine the mutual diffusion coefficient. The mutual diffusion coefficient is dependent of concentration, which is concluded from the asymmetry in the Cl- and Si-profiles. A linear dependence of the mutual diffusion coefficient on the composition is used as a first order approximation. The best fits are obtained for a value of b=(0.38+/-0.15), which is the ratio of the diffusion coefficient of 1,3-bis(3-methacryloxypropyl)-1, 1,3,3-tetramethyldisiloxane in pure 2-chloroethyl acrylate and the diffusion coefficient of 2-chloroethyl acrylate in pure 1,3-bis(3-methacryloxypropyl)-1,1,3,3-tetramethyldisiloxane. Under the assumption of a linear dependence of the mutual diffusion coefficient DV on monomer composition, it follows that DV = (2.9+/-0.6)10(-10) m(2)/s at a 1:1 monomer ratio. With Flory-Huggins expressions for the monomer chemical potentials, one can derive approximate values for the individual monomer diffusion coefficients.     

Hartree-Fock cluster study of interstitial transition metals in silicon

Results are presented of a Hartree-Fock cluster study of interstitial Ti, V, Cr, and Mn impurities in silicon. A Si₁₀ cluster models the nearest Si atoms around a tetrahedral interstitial site in crystalline Si. The dangling bonds of the Si atoms are saturated by hydrogens. The effect of the Si core electrons is represented by an effective potential. Characteristic for the electronic structure of the low-lying states of the neutral, singly positive, and doubly positive ions in silicon is the presence of fairly delocalized but still predominantly transition-metal (3d)-like orbitals of t₂ and e symmetry. For all ions the energy of the weighted average of the terms belonging to a configuration is lowest for the configuration with maximum occupation of the t₂ orbitals. Ground states with maximum spin multiplicity are found for all ions, except Ti⁰.     

Rearrangements and fragmentations of [C2H5S]+ ions

[C₂H₅S]⁺ ions (m/e 61) with different initial structures were generated in the mass spectrometer from twelve precursor ions. Abundance ratios of competing metastable ion decompositions were used to determine whether these ions decompose through the same or different reaction channels. It was concluded that all [C₂H₅S]⁺ ions isomerize to a common structure or mixture of structures prior to decomposition in the first field free region. From ¹³C labelling experiments it was concluded that [C₂H₅S]⁺ ions generated from the molecular ions of 2-propanethiol-2-[¹³C], partially rearrange to a symmetrical structure before decomposition to [CHS]⁺ and CH₄, whereas in [C₂H₅S]⁺ ions generated from the the molecular ions of 1,2-bis-(thiomethoxy-[¹³C]) ethane, the two carbon atoms become fully equivalent before CH₄ loss occurs.     

Hill's equation with quasi-periodic forcing: resonance tongues, instability pockets and global phenomena

A simple example is considered of Hill's equation , where the forcing termp, instead of periodic, is quasi-periodic with two frequencies. A geometric exploration is carried out of certain resonance tongues, containing instability pockets. This phenomenon in the perturbative case of small |b|, can be explained by averaging. Next a numerical exploration is given for the global case of arbitraryb, where some interesting phenomena occur. Regarding these, a detailed numerical investigation and tentative explanations are presented.Dedicated to the memory of Ricardo Mañé     

A Glassy Bending‐Mode Polymeric Actuator Which Deforms in Response to Solvent Polarity

Summary: We investigate a series of glassy polymer actuators which are found to bend rapidly and reversibly in response to changes in the solvent environment. The actuators are based on hydrogen‐bonded liquid crystal networks, and bending motion is created using director profiles engineered to take advantage of the network swelling anisotropy. Strongly polar solvents easily swell the network, forcing bending in one direction, while the less polar solvents extract water to force bending in the opposite direction.

Shape variation of twisted configuration liquid crystal polymer films in acetone and water.