Interaction of surfactant with antistatic polymer thin layers

Thin layers made from three kinds of hydrophilic polymer were coated onto poly(ethylene terephthalate)(PET) fibers to study the interaction of an anionic surfactant, sodiumn-dodecyl benzenesulfonate, with the polymer layers. The coated layers include a) poly(vinyl alcohol) (PVA) crosslinked with glutaraldehyde [nonionic], b) crosslinked, sulfated PVA [anionic], and c) polyethyleneimine crosslinked with poly(ethyleneglycol diglycidylether) [cationic]. All of these coatings were found to reduce the electrostatic charging of the PET cloths, indicating that they were effectively coated with the hydrophilic polymers. The PET cloth coated with the thin layers was immersed in the aqueous solution of surfactant at 40°C for different durations and the electrostatic voltage as well as the weight change were determined after drying. When the cloth coated with the nonionic or the anionic layer was brought into contact with the surfactant, neither the electrostatic voltage nor the weight of PET changed. On the contrary, immersion in the surfactant solution brought about an increase in both the electrostatic voltage and the weight for the PET coated with the cationic layer. This suggested that the surfactant molecules were bound to the cationic layer, in contrast to the nonionic and the anionic layer. It was concluded that the binding was due to ion complexing between the cationic groups in the polymeric layer and the sulfate groups in the surfactant molecules.     

The conduction switching effect in thin polymer layers

The effect of pressure-induced and field-induced conduction switching in thin polymer layers was experimentally studied. Conduction switching was observed in thin layers of poly(diphenylene phthalide), polyvinylcarbazole, some aromatic polyimides, and methoxypoly(phenylene-vinylene). It was found that conduction switching depends in a critical manner on the formation mode of the metal/polymer contact.     

Molecular dynamics in thin (grafted) polymer layers

Broadband dielectric spectroscopy is employed to study the molecular dynamics in thin polymer layers of (spin-coated) cis-1, 4-polyisoprene (PI) and of (grafted and spin-coated) polydimethylsiloxane (PDMS). For the former, besides the segmental and the normal mode relaxation, a confinement-induced mode is observed, which is assigned to fluctuations of terminal subchains. It turns out that the uptake of water has a strong influence on the dynamics of this relaxation, which takes place in the immediate vicinity of the interface. Between grafted and spin-coated PDMS a pronounced difference in the dynamics is observed for layers that are comparable in thickness to the radius of gyration of the confined chain. This is attributed to the different conformation of grafted and spin-coated polymer layers.     

Surface plasmon near-field imaging of very thin microstructured polymer layers

We report on the near-field imaging of microstructured polymer layers deposited on an homogeneous metal thin film on which a surface plasmon mode is excited. The microstructures in the polymer layers are designed by electron beam lithography, and the near-field imaging is performed with a photon scanning tunneling microscope (PSTM). We show that, despite their very small height, the microstructures can be conveniently imaged with a PSTM thanks to the field enhancement at the surface of the metal thin film supporting the surface plasmon. The influence of the illumination conditions on the contrast of the PSTM images is discussed. In particular, we show that both the field enhancement and the near-field intensity distribution around the microstructures depend dramatically upon the illumination conditions, leading to the conclusion that the PSTM is well suited for spatially resolved near-field surface plasmon sensing purposes.     

Computer simulations of energetic and conformational changes in polymer systems

Using a Monte Carlo method, the deformation behavior of single polymer coils was investigated. Random walks were used to verify the stretching procedure. The prediction of Pincus and DeGennes for self avoiding walks could be confirmed. The simulations at finite temperatures showed a transition from entropy to energy controlled behavior. The coils underwent a clear nonaffine deformation pattern.     

Computer simulations of stretching and collapse of polymer molecules in solution

Computer simulations are reported for system of linear polymer molecules, diblock copolymer and dendrimer in dilute solution without and with elongational flow. The effect of fluctuating hydrodynamics interactions (HI) on the coil-stretch transition of linear polymers and dendrimers in elongational flow is studied. The process of coiling of homo- and blockcopolymer from completely extended state is also simulated.     

Self-assembly of polymer layers with mobile grafting points: Computer simulation

The Monte Carlo method is used to study macromolecule layers with mobile grafting points during deterioration in the solvent quality. If the chains are rigidly grafted onto the surface, the micelle core is bonded to the surface through chain fragments that are strongly extended along the surface, but if the points are fairly mobile, the micelles are dense aggregates maximally segregated from the surface. In addition, an increase in the mobility of the chains leads to increase in the mean aggregation number of the micelles, its dispersion, and height of the aggregate.     

Nano-organized collagen layers obtained by adsorption on phase-separated polymer thin films

The organization of adsorbed type I collagen layers was examined on a series of polystyrene (PS)/poly(methyl methacrylate) (PMMA) heterogeneous surfaces obtained by phase separation in thin films. These thin films were prepared by spin coating from solutions in either dioxane or toluene of PS and PMMA in different proportions. Their morphology was unraveled combining the information coming from X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and water contact angle measurements. Substrates with PMMA inclusions in a PS matrix and, conversely, substrates with PS inclusions in a PMMA matrix were prepared, the inclusions being either under the form of pits or islands, with diameters in the submicrometer range. The organization of collagen layers obtained by adsorption on these surfaces was then investigated. On pure PMMA, the layer was quite smooth with assemblies of a few collagen molecules, while bigger assemblies were found on pure PS. On the heterogeneous surfaces, it appeared clearly that the diameter and length of collagen assemblies was modulated by the size and surface coverage of the PS domains. If the PS domains, either surrounding or surrounded by the PMMA phase, were above 600 nm wide, a heterogeneous distribution of collagen was found, in agreement with observations made on pure polymers. Otherwise, fibrils could be formed, that were longer compared to those observed on pure polymers. Additionally, the surface nitrogen content determined by XPS, which is linked to the protein adsorbed amount, increased roughly linearly with the PS surface fraction, whatever the size of PS domains, suggesting that adsorbed collagen amount on heterogeneous PS/PMMA surfaces is a combination of that observed on the pure polymers. This work thus shows that PS/PMMA surface heterogeneities can govern collagen organization. This opens the way to a better control of collagen supramolecular organization at interfaces, which could in turn allow cell-material interactions to be tailored.     

Characterization of thin polymer and biopolymer layers by ellipsometry and evanescent field technology

The characterization of sensitive layers is the prerequisite for the optimization of chemical and biochemical sensors. The application of SE (Spectral Ellipsometry) and SPR (Surface Plasmon Resonance) as methods of characterization of such sensitive layers is discussed. In combination with infrared spectroscopy, the properties of polymer networks, micro-porous polymers, liquid crystals, and biomimetic polymers can be examined regarding their applicability for optical sensing. Apart from the basic principles regarding the characterization approaches, applications in the area of environmental sensing, optimization of hydrogel layers for antigen/antibody interaction, and discrimination of analytes in homologous series of alcohols are discussed. The effects of analytes on the phase transition in combination with disordering of liquid crystals are given.     

Computer simulations of polymer chain structure and dynamics on a hypersphere in four-space

There is a rapidly growing interest in performing computer simulations in a closed space, avoiding periodic boundary conditions. To extend the range of potential systems to include also macromolecules, we describe an algorithm for computer simulations of polymer chain molecules on S3, a hypersphere in four dimensions. In particular, we show how to generate initial conformations with a bond angle distribution given by the persistence length of the chain and how to calculate the bending forces for a molecule moving on S3. Furthermore, we discuss how to describe the shape of a macromolecule on S3, by deriving the radius of gyration tensor in this non-Euclidean space. The results from both Monte Carlo and Brownian dynamics simulations in the infinite dilution limit show that the results on S3 and in R3 coincide, both with respect to the size and shape as well as for the diffusion coefficient. All data on S3 can also be described by master curves by suitable scaling by the corresponding values in R3. We thus show how to extend the use of spherical boundary conditions, which are most effective for calculating electrostatic forces, to polymer chain molecules, making it possible to perform simulations on S3 also for polyelectrolyte systems.     

Computer simulations of photoionization

The Energy Distribution of Ionizing Transitions (EDIT) for (Cs₂O) _n clusters has been calculated using the technique of molecular dynamics. Isomerization, thermal atomic motion and the electronic density of states all contribute to the shape of these curves.     

Insights into thin, thermally responsive polymer layers through quartz crystal microbalance with dissipation

The thermodynamics of temperature-responsive polymeric layers was analyzed using a two-state coil to globule model to which the van't Hoff relationship was applied. For soluble homopolymer poly(N-isopropylacrylamide (pNIPAAm), enthalpies of transition, ΔH(vH), were calculated using varations in ultraviolet-visible (UV-vis) spectroscopy with temperature to be 8400 ± 30 and 1652 ± 4 kJ mol-cooperative unit(-1) for standard synthesis and initiated chemical vapor deposition (iCVD), respectively. For the insoluble surface-bound layer of cross-linked iCVD poly(N-isopropylacrylamide-co-di(ethylene glycol) divinyl ether) [p(NIPAAm-co-DEGDVE)], ΔH(vH) was determined to be 810 ± 30 kJ mol-cooperative unit(-1) using quartz crystal microbalance with dissipation monitoring (QCM-D). Microcalorimetry measurements showed the enthalpies per mole NIPAAm monomer to be 5.8 ± 0.2, 3.5 ± 0.6, and 3.1 ± 0.3 kJ mol-NIPAAm(-1), resulting in cooperative unit sizes of 1460 ± 60, 470 ± 80, and 260 ± 30 monomer units for the standard pNIPAAm, iCVD pNIPAAm, and p(NIPAAm-co-DEGDVE) systems, respectively. These values indicate that both per monomer enthalpic contribution as well as cooperative unit size are primary factors contributing to the variations in van't Hoff enthalpies for the three systems studied. Diffusion of bovine serum albumin (BSA) into swollen p(NIPAAm-co-DEGDVE) films below its lower critical solution temperature was elucidated via QCM-D measurements. These data provided a calculated diffusion coefficient of (3.5 ± 0.1) × 10(-14) cm(2) s(-1) of BSA into the swollen hydrogel film with a mesh size of 6.0 ± 0.2 nm (compared to the hydrodynamic radius of BSA, r(H) = 3.36 nm).     

Synthesis of polymer dielectric layers for organic thin film transistors via surface-initiated ring-opening metathesis polymerization

The use of surface-initiated ring-opening metathesis polymerization (SI-ROMP) for producing polymer dielectric layers is reported. Surface tethering of the catalyst to Au or Si/SiO2 surfaces is accomplished via self-assembled monolayers of thiols or silanes containing reactive olefins. Subsequent SI-ROMP of norbornene can be conducted under mild conditions. Pentacene semiconducting layers and gold drain/source electrodes are deposited over these polymer dielectric films. The resulting field effect transistors display promising device characteristics, demonstrating for the first time that SI-ROMP can be used in the construction of organic thin-film electronic devices.     

Computer simulations of micellar systems

Works published during the last decade devoted to simulation of micellar solutions of different surfactants are reviewed. The main attention is focused on studying the local structure of spherical and cylindrical micelles and their surface layers in solutions, as well as problems relevant to self-aggregation kinetics.     

Computer simulations of nematic droplets

Abstract

Nematic droplets are intimately connected with disclinations, because in nematic droplets, point and line-shaped defects, as well as surface defects, are not generated at random, but inevitably by topological constraints. Thus, droplets provide a good means for investigating nematic defects. There is a growing interest in both topics due to the applications in polymer dispersed liquid crystal devices [1–3], but also in classical display modelling, where nematic defects are to be avoided. Various types of droplets are investigated theoretically with the aid of a previously developed numerical algorithm [4,5], which is based on a dynamic equation for the alignment tensor a _μv. The rotational diffusion, the influence of an orienting external field, and the Frank elasticity (in the one-coefficient approximation) are taken into account, but flow processes are neglected. For the application to nematic droplets, a new type of boundary conditions had to be used, which I have called ‘true planar anchoring’. I simulate the relaxation of the director field of nematic droplets from the isotropic state and vice versa for various types of anchoring and cavity shapes. Contrast pictures, as if viewed under crossed Nicols, are computed and compared to experiment. The results obtained elucidate the nature of the surface disclinations of strength one (boojums). In particular, it is found that their occurrence can be understood as a consequence of the planar anchoring, without any further assumptions. Moreover, a phase transition-like transformation of the director configuration is predicted which is temperature controlled and occurs, as the blue phases do, close to the nematic-isotropic transition temperature T_c.     

Oscillations in thin nematic layers

In the present paper a thin nematic liquid crystal layer between two identical boundary surfaces (solid walls or free surfaces in the case of a freely suspended film) is considered. In a mean field approximation it is shown that the interference between the boundary surface-induced smectic density waves results in oscillations of the free energy of the nematic layer and disjoining pressure acting on the boundary surfaces. Theoretical dependence of disjoining pressure on the nematic layer thickness is in qualitative agreement with experiment. Also we have considered a thin film of polar nematic in which in addition to an ordinary monolayer smectic A phase (S_A1) with the layer thickness d equal to the molecular length l the partial bilayer smectic A phase (S_Ad) occurs. It is shown that the variation of the distance between the boundary surfaces can result in the oscillatory S_A1-A_Ad phase transitions in this nematic film     

Electrocatalytic aspects of electrogenerated polymer layers

Two main aspects of electrocatalysis of electrogenerated polymer layers (polypyrrole in this case) are presented here. The first aspect concerns the electrogenerated conducting polypyrrole layer as such; i.e. its preparation with built-in electrocatalysts, like Pt or metal-organic complexes. Its properties are discussed in terms of their real electrocatalytic behaviour, viz. their turn-over numbers. The second part deals with specific studies like: - the anodic oxidation of hydrogen with built-in Pt, and, - the cathodic reduction of oxygen with Co and/or Fe-phthalocyanines. The theoretical model predicts rather well the experimental behaviour.     

Deposition of thin electroplated Cd-Se layers

Cadmium-selenium alloys were electrodeposited from a sulfuric acid electrolyte. The effect of the H₂SeO₃, CdSO₄, and sulfuric acid concentrations, current density, and temperature on the composition and quality of cathode deposits was studied.