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The influence of polyelectrolytes on structure formation in liquid crystalline Na-dodecylsulfate/decanol/water systems was investigated by means of small angle X-ray diffraction, rheology, NMR spectroscopy, and microscopy. By adding Na-polyacrylate (PAA) into the mesophase, the one-phase region is left and phenomena of phase separation into a solvent-rich and a polymer/surfactantrich phase occurs. By incoporating an anionic and cationic polyelectrolyte step by step the tendency of phase separation is increased drastically. The self-organization process can be regulated directly by varying the water content of the system. However, at a water content of 30% the properties of the resulting liquid crystal were changed drastically. X-ray diffraction shows a multitude of Bragg peaks, NMR shows a peak-splitting, and rheology shows a change from non-Newtonian to Newtonian-flow behavior. On the basis of the experimental results an ordered multilayer associate structure can be assumed.
The paper is focused on the formation and redispersion of monodisperse BaSO4 nanoparticles in polyelectrolyte- modified microemulsions. It is shown that a cationic polyelectrolyte of low molar mass, e.g. poly(dially1dimethylammonium chloride) (PDADMAC), can be incorporated into the individual inverse microemulsion droplets (L2 phase) consisting of heptanol, water, and an amphoteric surfactant with a sulfobetaine head group. These PDADMAC- filled microemulsion droplets can be successfully used as a template phase for the nanoparticle formation. The monodisperse BaSO4 nanoparticles are produced by a simple mixing procedure and can be redispersed after solvent evaporation without a change in particle dimensions. Dynamic and electrophoretical light scattering in combination with sedimentation experiments in the analytical Ultracentrifuge of the redispersed powder show polyelectrolyte-stabilized nanoparticles with diameters of about 6 nm. The polyelectrolyte shows a "size control effect", which can be explained by the polyelectrolyte-surfactant interactions in relation to the polyelectrolyte-nanoparticle interactions during the particle growth, solvent evaporation and redispersion process. However, the approach used here opens away to produce different types of polyelectrolyte-stabilized nanoparticles (including rare metals, semiconductors, carbonates or oxides) of very small dimensions. (C) 2004 Elsevier B.V. All rights reserved
Polymer-induced structural changes in lecithin/sodium dodecyl sulfate-based multilamellar vesicles
(2004)
Aqueous concentrated lecithin mixtures (asolectin from soybean) show typical lamellar liquid crystalline behavior and the individual lamellae tend to form spherical supramolecular structures, i.e., multilamellar vesicles. When part of the lecithin is replaced by the anionic surfactant sodium dodecyl sulfate (SIDS), the compact multilamellar vesicles disappear and the viscosity decreases. By adding oly(diallyldimethylammonium chloride) (PDADMAC) to the lecithin/SDS system, the formation of multilamellar vesicles can be induced again and the viscosity increases. However, one characteristic feature of these polymer-modified systems is a temperature-dependent phase transition from a compact multilamellar vesicle phase to a more swollen liquid crystalline phase. The polymer-modified multilamellar compact vesicles are of interest for utilization as new thermosensitive drug delivery systems. (C) 2003 Elsevier Inc. All rights reserved
Materials for polymer electronics applications semiconducting polymer thin films and nanoparticles
(2004)
The paper presents two different approaches to nanostructured semiconducting polymer materials: (i) the generation of aqueous semiconducting polymer dispersions (semiconducting polymer nanospheres SPNs) and their processing into dense films and layers, and (ii) the synthesis of novel semiconducting polyfluorene-block-polyaniline (PF-b-PANI) block copolymers composed of conjugated blocks of different redox potentials which form nanosized morphologies in the solid state
In cellular, electromechanically active polymer films, the so-called ferroelectrets, the cell size and shape distributions can be varied through a controlled inflation process. Up to now, high-pressure treatments were usually performed at elevated temperatures. There are, however, significant experimental limitations and complications if the pressure and temperature treatments are performed at the same time. Here, we demonstrate the controlled inflation of cellular polypropylene films by means of sepal-ate pressure and temperature treatments. Separate procedures are Much easier to implement. Excellent electromechanical properties were achieved with Such a two-step inflation process. The technique has significant potential for inflating large-area transducer films for electromechanical and electroacoustical applications
This paper is focused on the synthesis and characterization of hydrophobically modified polyelectrolytes and their use as reducing as well as stabilizing agents for the formation of gold nanoparticles. Commercially available poly(acrylic acid) has been hydrophobically modified with various degrees of grafting of butylamine introduced randomly along the chain. Different analytical methods are performed, i.e., IR and H-1-NMR spectroscopy in combination with elemental analysis to determine the degree of grafting. The modified polymers can successfully be used for the controlled single-step synthesis and stabilization of gold nanoparticles. The process of nanoparticle formation is investigated by means of UV-vis spectroscopy. The size and shape of the particles obtained in the presence of unmodified or modified polyelectrolytes are characterized by dynamic light scattering, zeta potential measurements and transmission electron microscopy. The polyelectrolytes were involved in the crystallization process of the nanoparticles, and in the presence of hydrophobic microdomains at the particle surface, a better stabilization at higher temperature can be observed
This paper presents some results concerning the size-controlled hydroxyapatite nanoparticles obtained in aqueous media in a biopolymer matrix from soluble precursors salts. Taking the inspiration from nature, where composite materials made of a polymer matrix and inorganic fillers are often found, e.g. bone, shell of crustaceans, shell of eggs, etc., the feasibility on making composite materials containing chitosan and nanosized hydroxyapatite was investigated. A stepwise co-precipitation approach was used to obtain different types of composites by means of different ratio between components. The synthesis of hydroxyapatite was carried out in the chitosan matrix from calcium chloride and sodium dihydrogenphosphate in alkaline solutions at moderate pH of 10-11 for 24 h. Our research is focused on studying and understanding the structure of this class of composites, aiming at the development of novel materials, controlled at the nanolevel scale. The X-ray diffraction technique was employed in order to study the kinetic of hydroxyapatite formation in the chitosan matrix as well as to determine the HAp crystallite sizes in the composite samples. The hydroxyapatite synthesized using this route was found to be nano-sized (15-50nm). Moreover, applying an original approach to analyze the (002) XRD diffraction peak profile of hydroxyapatite by using a sum of two Gauss functions, the bimodal distribution of nanosized hydroxyapatite within the chitosan matrix was revealed. Two types of size distribution domains such as cluster-like (between 200 and 400 nm), which are the habitat of "small" hydroxyapatite nanocrystallites and scattered-like, which are the habitat of "large" hydroxyapatite nanocrystallites was probed by TEM and CSLM. The structural features of composites suggest that self-assembly processes might be involved. The composites contain nanosized hydroxyapatite with structural features close to those of biological apatites that make them attractive for bone tissue engineering applications. (c) 2005 Elsevier Ltd. All rights reserved
This paper focuses on the characterization and use of polymer-modified phosphatidylcholine (PC)/sodium dodecyl sulfate (SDS)-based inverse microemulsions as a template phase for BaSO4 nanoparticle formation. The area of the optically clear inverse microemulsion phase in the isooctane/hexanol/water/PC/SDS system is not significantly changed by adding polyelectrolytes, i.e., poly(diallyldimethylammonium chloride) (PDADMAC), or amphoteric copolymers of diallyldimethylammonium chloride and maleamid acid to the SDS-modified inverse microemulsion. Shear experiments show non- Newtonian flow behavior and oscillation experiments show a frequency-dependent viscosity increase (dilatant behavior) of the microemulsions. Small amounts of bulk water were identified by means of differential scanning calorimetry. One can conclude that the macromolecules are incorporated into the individual droplets, and polymer-filled microemulsions are formed. The polymer-filled microemulsions were used as a template phase for the synthesis of BaSO4 nanoparticles. After solvent evaporation the nanoparticles were redispersed in water and isooctane, respectively. The polymers incorporated into the microemulsion are involved in the redispersion process and influence the size and shape of the redispersed BaSO4 particles in a specific way. The crystallization process mainly depends on the type of solvent and the polymer component added. In the presence of the cationic polyelectrolyte PDADMAC the crystallization to larger cubic crystals is inhibited, and layers consisting of polymer-stabilized spherical nanoparticles of BaSO4 (6 nm in size) will be observed. (c) 2004 Elsevier Inc. All rights reserved
The influence of the water soluble polymer poly(ethylene glycol) (PEG) on structure formation in the quasiternary system sodium dodecylsulfate (SDS)/pentanol-xylene/water was checked by means of conductometry, rheology, and micro differential calorimetry. The polymer induces the formation of an isotropic phase channel between the o/w and w/o microemulsion. The transition from the normal as well as from the inverse micellar to the bicontinuous phase range can be detected by conductometry, rheology as well as micro-DSC. As a result of polymer-surfactant interactions, the spontaneous curvature of the surfactant film is changed and a sponge phase is formed. The bicontinuous phase is characterized by a moderate shear viscosity, a Newtonian flow behaviour, and the disappearence of interphasal water in the heating curve of the micro-DSC. When the polymer-modified bicontinuous phase is used as a template phase for the nanoparticle formation, spherical BaSO4 nanoparticles were formed. During the following solvent evaporation process the primarily formed spherical nanoparticles aggregate to nanorods and triangular structures due to the non-restriction of the bicontinuous template phase in longitudinal direction
Electrically charged porous polytetrafluoroethylene (PTFE) films are often discussed as active layers for electromechanical transducers. Here, the electric charging behavior of open-porous PTFE films with different porosities is investigated. Optimized electric charging of porous PTFE films is determined by variation of charging parameters such as electric fields and charging times. Maximum surface potentials are depending on the porosity of the PTFE films. Suitable charging leads to high surface potentials observed on non-stretched or slightly stretched porous PTFE films. Further increase of charging fields yields decreasing values of the surface potential accompanied with an increase of conductivity.
The epoxy system containing diglycidyl ether of bisphenol A and 4,4'-diaminodiphenyl sulfone is modified with poly(acrylonitrile-butadiene-styrene) (ABS) to explore the effects of the ABS content on the phase morphology, mechanism of phase separation, and viscoelastic properties. The amount of ABS in the blends was 5, 10, 15, and 20 parts per hundred of epoxy resin (phr). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were employed to investigate the final morphology of ABS-modified epoxy blends. Scanning electron microscopic studies of 15 phr ABS-modified epoxy blends reveal a bicontinuous structure in which both epoxy and ABS are continuous, with substructures of the ABS phase dispersed in the continuous epoxy phase and substructures of the epoxy phase dispersed in the continuous ABS phase. TEM micrographs of 15 phr ABS-modified epoxy blends confirm the results observed by SEM. TEM micrographs reveal the existence of nanosubstructures of ABS in 20 phr ABS-modified epoxy blends. To the best of our knowledge, to date, nanosubstructures have never been reported in any epoxy/thermoplastic blends. The influence of the concentration of the thermoplastic on the generated morphology as analyzed by SEM and TEM was explained in detail. The evolution and mechanism of phase separation was investigated in detail by optical microscopy (OM) and small-angle laser light scattering (SALLS). At concentrations lower than 10 phr the system phase separates through nucleation and growth (NG). However, at higher concentrations, 15 and 20 phr, the blends phase separate through both NG and spinodal decomposition mechanisms. On the basis of OM and SALLS, we conclude that the phenomenon of complex substructure formation in dynamic asymmetric blends is due to the combined effect of hydrodynamics and viscoelasticity. Additionally, dynamic mechanical analysis was carried out to evaluate the viscoelastic behavior of the cross-linked epoxy/ABS blends. Finally, apparent weight fractions of epoxy and ABS components in epoxy- and ABS-rich phases were evaluated from T-g analysis.
This work is focused on the influence of an ionic liquid (IL), i.e. ethyl-methylimidazolium hexylsulfate, on the spontaneous formation of microemulsions with ionic surfactants. The influence of the ionic liquid on Structure formation in the optically clear phase region in water/toluene/pentanol mixtures in presence of the cationic surfactant CTAB was studied in more detail. The results show a significant increase of the transparent phase region by adding the ionic liquid. Conductometric investigations demonstrate that adding the ionic liquid can drastically reduce the droplet- droplet interactions in the L-2 phase. H-1 nuclear magnetic resonance (H-1 NMR) diffusion coefficient measurements in combination with dynamic light scattering measurements clearly show that inverse microemulsion droplets still exist, but the droplet size is decreased to 2 nm. A more detailed characterisation of the isotropic phase channel by means of conductivity measurements, dynamic light scattering (DLS), H-1 NMR and cryo-scanning electron microscopy (SEM), allows the identification of a bicontinuous sponge phase between the L-1 and L-2 phase. When the poly(ethyleneimine) is added, the isotropic phase range is reduced drastically, but the inverse microemulsion range still exists.
Polymer-modified bicontinuous microemulsions used as a template for the formation of nanorods
(2009)
This article is focused on the characterization of the poly(ethylene glycol) (PEG)-induced bicontinuous microemulsion of the pseudo-ternary system sodium dodecylsulfate (SDS)/xylene-pentanol/water by means of differential scanning calorimetry, rheology, and conductometry. The influence of the polymer concentration (cp) and the molecular weight (Mw) on the microstructure of the microemulsion was investigated using Cryo scanning electron microscopy. It was found that an increase of cp influences the structure of the sponge-like phase significantly. These polymer-modified microemulsions can be used as a template phase for the formation of BaSO4 nanorods, where individual nanoparticles (5nm in size) are ordered along the polymer backbone.