Search results for "surface"
showing 10 items of 9345 documents
Glass transition of polymer melts: Test of theoretical concepts by computer simulation.
2003
Abstract Polymers are good glass formers and allow for the study of melts near the glass transition in (meta-)stable equilibrium. Theories of the glass transition imply such an equilibrium and can, hence, be tested by the study of polymer melts. After a brief summary of the basic experimental facts about the glass transition in polymers, the main theoretical concepts are reviewed: mode coupling theory (MCT), entropy theory, free-volume theory, the idea of a growing length describing the size of cooperative regions, etc. Then, two basic coarse-grained models of polymers are described, which have been developed aiming at a test of these concepts. The first model is the bond-fluctuation model …
Interfaces between coexisting phases in polymer mixtures: What can we learn from Monte Carlo simulations?
1999
Symmetric binary polymer mixtures are studied by Monte Carlo simulation of the bond fluctuation model, considering both interfaces between coexisting bulk phases and interfaces confined in thin films. It is found that the critical behavior of interfacial tension and width is compatible with that of the Ising model, as expected from the universality principle. In the strong segregation limit, only qualitative but not quantitative agreement with the self-consistent field (SCF) theory is found. It is argued that the SCF theory requires √ 6 X √D for short-range forces, in agreement with experiment.
Spectroscopic and structural characterization of pure and FeCl3-containing tri-n-butyl phosphate
2014
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3 − n ] n+ and FeCl4 − complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attri…
Microstructure and lateral diffusion in monolayers of polymerizable amphiphiles
1989
Lipid analogue amphiphilic molecules containing polymerizable units were investigated in monolayers at the air/water interface by using film balance measurements, fluorescence microscopy, and photobleaching techniques. The polymerizable groups (diene-, diyne-, and methacrylate units) were introduced into the hydrophobic alkyl chains or into the polar head of the amphiphilic molecules. In the case of the diene- and diyne-containing compounds the polymerizable units are incorporated into the hydrophobic alkyl chains, enabling them to form a two-dimensional network. Due to the free chain flexibility of the monomers the lateral mobility was comparable to that of saturated lipid analogues and de…
Hydrogen bonds in unpolar matrix — Comparison of complexation in polymeric and low molecular-weight systems
1991
By ene-reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with double bonds, polar 4-phenyl-1,2,4-triazolidine-3,5-dione (phenyl urazole) groups are introduced into unpolar matrices. Hydrogen-bond complexes are formed between two amide-like units. The temperature dependence of complex formation in dilute hydrocarbon medium is obtained from remperature-dependent IR spectra in the region of the C=O stretching vibration. Results obtained for a low molecular-weight model system are compared with modified polybutadienes, where the groups are attached statistically along the polymer backbone. The enthalpy and the entropy of complex formation (ΔH f =−28.6 kJ/mol; ΔS f =−52 J/mol K−1) obtained for the…
Reactions of Maleisomides with Alcohols
2004
Abstract New surfactants (surfmers) with various amide and ester groups next to C˭C double bonds have been obtained. Maleic acid amidesters (AE) with different hydrophobic groups at the nitrogen atom and hydrophilic substituents at oxygen atoms were synthesized starting with maleic isoimides. 1H KMR and IR spectra were used for their characterization. Some were further characterized for their critical micellar concentration (CMC). A few cationic and zwitterionic surfmers were also prepared from isoimide precursors and characterized. All these surfmers were applied in batch emulsion polymerization of styrene, and in core‐shell seeded copolymerization of styrene and butylacrylate to give late…
Polymer supported synthesis of mixed ligand complexes
2003
A series of novel polymer-supported mixed ligand complexes were synthesized and studied. Two percent divinyl benzene (DVB)-crosslinked polystyrene supports were synthesized by the suspension copolymerization technique. An ethylene diamine group was anchored onto the support and the corresponding copper complexes were prepared. The ligating functions like phthalate, acetate, and oxalate groups were introduced, and mixed ligands complexes were synthesized. The resultant polymer supported mixed ligand complexes were characterized by UV-Vis, IR, and EPR methods. The stability constants dictate the formation of these complexes on polymer support. Spectral results gave information about the struc…
Cationic copolymers of ?,?-poly-(N-2-hydroxyethyl)-DL-aspartamide (PHEA) and ?,?-polyasparthylhydrazide (PAHy): synthesis and characterization
2000
In the present study the derivatization of two water-soluble synthetic polymers, α,β-poly(N-2-hydroxyethyl)-DL-aspartamide (PHEA) and α,β-polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introdu…
Versatile ω-end group functionalization of RAFT polymers using functional methane thiosulfonates
2009
Five different polymers, poly[methyl methacrylate] (PMMA), poly[lauryl methacrylate] (PLMA), poly[diethylene glycol methacrylate] (PDEGMA), poly[N-iso-propylacrylamide] (PNIPA), and poly[styrene] (PS) prepared by the RAFT process and thus terminated with dithioesters were aminolyzed in the presence of S-3-butynyl methane thiosulfonate (MTS), which was synthesized in two steps. Analysis of the polymers by 2D NMR, UV–vis absorbance, and gel permeation chromatogra-phy revealed them to quantitatively carry acetylene end groups connected with disul-fide bridges, indicating that functional MTS reagents can be employed for end group functionalization of RAFT polymers. This versatile method is of ad…
Computer simulation of macromolecular materials
1988
Computer simulation of model systems with Monte Carlo methods enables the detailed study of structure and thermodynamic properties of these systems and thus constitutes a link between analytic theory and experiment. Typical applications that are discussed include polymer blends, dynamics of local motions in polymer melts, and the adsorption of polymers on walls.