Abstract: The solid-state organization of a benzothiadiazole-cyclopentadithiophene copolymer with long, branched decyl-tetradecyl side chains (CDT-BTZ-C14,10) is investigated. The C14,10 substituents are sterically demanding and increase the π-stacking distance to 0.40 nm from 0.37 nm for the same polymer with linear hexadecyls (C16). Despite the bulkiness, the C14,10 side chains tend to crystallize, leading to a small chain-to-chain distance between lamellae stacks and to a crystal-like microstructure in the thin film. Interestingly, field-effect transistors based on solution processed layers of CDT-BTZ-C14,10 show ambipolar behavior in contrast to CDT-BTZ-C16 with linear side chains, for which hole transport was previously observed. Due to the increased π-stacking distance, the mobilities are only 6 × 10−4 cm²/Vs for electrons and 6 × 10−5 cm²/Vs for holes, while CDT-BTZ-C16 leads to values up to 5.5 cm²/Vs. The ambipolarity is attributed to a lateral shift between stacked backbones provoked by the bulky C14,10 side chains. This reorganization is supposed to change the transfer integrals between the C16 and C14,10 substituted polymers. This work shows that the electronic behavior in devices of one single conjugated polymer (in this case CDT-BTZ) can be controlled by the right choice of the substituents to place the backbones in the desired packing.
Abstract: The mechanical and physical properties of polymeric materials originate from the interplay of phenomena at different spatial and temporal scales. As such, it is necessary to adopt multiscale techniques when modeling polymeric materials in order to account for all important mechanisms. Over the past two decades, a number of different multiscale computational techniques have been developed that can be divided into three categories: (i) coarse-graining methods for generic polymers; (ii) systematic coarse-graining methods and (iii) multiple-scale-bridging methods. In this work, we discuss and compare eleven different multiscale computational techniques falling under these categories and assess them critically according to their ability to provide a rigorous link between polymer chemistry and rheological material properties. For each technique, the fundamental ideas and equations are introduced, and the most important results or predictions are shown and discussed. On the one hand, this review provides a comprehensive tutorial on multiscale computational techniques, which will be of interest to readers newly entering this field; on the other, it presents a critical discussion of the future opportunities and key challenges in the multiscale modeling of polymeric materials and how these methods can help us to optimize and design new polymeric materials.
Abstract: Plant petioles and stems are hierarchical cellular structures, displaying structuralfeatures defined at multiple length scales. The current work focuses on the multi-scalemodelling of plant tissue, considering two orders of structural hierarchy, cell wall and tissue.The stiffness of plant tissue is largely governed by the geometry of the tissue cells, thecomposition of the cell wall and the structural properties of its constituents. The cell wallis analogous to a fiber reinforced composite, where the cellulose microfibril (CMF) is theload bearing component. For multilayered cell wall, the microfibril angle (MFA) in themiddle layer of the secondary cell wall (S2 layer) largely affects the longitudinal stiffnessfor values up to 40o. The MFA in turn influences the overall wall stiffness. In this work,the effective stiffness of a model system based on collenchyma cell wall of a dicotyledonousplant, the Rheum rhabarbarum, is computed considering generic MFA and volume fractions.At the cellular level, a 2-D Finite Edge Centroidal Voronoi tessellation (FECVT) has beendeveloped and implemented to generate the non-periodic microstructure of the plant tissue.The effective elastic properties of the cellular tissue are obtained through finite elementanalysis (FEA) of the Voronoi model coupled with the cell wall properties. The stiffness ofthe hierarchically modeled tissue is critically important in determining the overall structuralproperties of plant petioles and stems.
Abstract: This paper describes the Z-RAFT-star copolymerization of n-butyl acrylate (BA) and N-isopropyl acrylamide (NIPAm), respectively, with N-ethylacrylate-3,4-dimethylmaleimide (1.1), a monomer carrying a UV-reactive unit that undergoes photocrosslinking. Addition of 1.1 slows down the polymerization rate both for BA and for NIPAm polymerization. Double star formation due to radical attack to the 3,4-dimethylmaleimide moiety was found in the case of BA. Dead polymer formation, presumably due to aminolysis as side-reaction, was pronounced in the NIPAm system. These two effects broadened the molar mass distributions, but did not impede the formation of functional star polymers. The composition of the copolymers as well as the reactivity ratios for the applied comonomers were determined via NMR spectroscopy (BA-co-1.1r1.1 = 2.24 rBA = 0.95; NIPAm-co-1.1r1.1 = 0.96 rNIPAm = 0.05). In both cases, the comonomer is consumed preferably in the beginning of the polymerization, thus forming gradient copolymer stars with the UV-reactive units being located in the outer sphere.
Abstract: Layer-by-layer (LbL) films were prepared over an aperture (diameter 1–5 mm) on a glass plate to study ion permeation across free-suspended LbL films. LbL films were prepared by depositing alternating layers of poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) on the surface of a glass plate with an aperture filled with an alginate gel, followed by dissolution of the alginate gel. PAH-PSS films prepared in this way showed permeability to inorganic salts, depending on the size and charge. Permeability to alkali metal chlorides depended on the Stokes radius of the alkali metal cations. The effect of the type of halide was negligible because of the halides’ smaller ionic radii. Permeation of multivalent ions such as Ru(NH3)63+ and [Fe(CN)6]3− was severely suppressed owing to Donnan exclusion.
Abstract: Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA), with poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine) (P4VP) blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS) corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.