Quartz crystal microbalance studies of polymer gels and solutions in liquid environments

Spreading of liquids and soft solids on a rigid surface in a surrounding liquid medium is investigated by utilizing the lateral sensitivity of the quartz crystal microbalance (QCM). While the QCM has been used extensively to study systems with spatial variations in the direction normal to the crystal's electrodes, few studies have exploited the QCM's ability to sense changes in loading in the plane of the electrodes. We propose equations to describe the predicted response of the QCM to a generalized viscoelastic material spreading at the QCM surface at the expense of the surrounding liquid medium. Several experimental examples are given in order to support the validity of the proposed equations, including situations where the spreading material is a Newtonian liquid, a viscoelastic liquid, or one of two viscoelastic solids. The first viscoelastic solid is a physically cross-linked gel based on a styrene/ethylene-butene/styrene triblock copolymer in mineral oil, and the second is a cross-linked poly(ethylene glycol) hydrogel.     

Role of template and infiltration technique on resulting morphology of polymer nanostructures

Polymer nanotubes are commonly fabricated using the template-assisted method. In the present study, polystyrene nanotubes were formed through a unique dipping technique that has not previously been reported. Anodized aluminum (AAO) templates were synthesized and infiltrated with polystyrene-tetrahydrofuran solutions. The effects of the template, polymer molecular weight and concentration on the final morphology were examined. The results indicate that stable nanotubes can be formed in homemade and commercial templates with polymer concentrations as low as 0.5 wt%. Nanotubes also resulted from a range of molecular weights indicating that the infiltration technique may be the primary factor enabling the formation of hollow structures.     

Quantitative study of the dispersion degree in carbon nanofiber/polymer and carbon nanotube/polymer nanocomposites

Quantitative measurements of the filler dispersion degree of carbon nanofiber (CNF) and nanotube (CNT) reinforced polymer nanocomposites have been made by transmission electron microscopy. Samples were prepared by either high-shear mixing or twin-screw extrusion processing. It was found that the filler dispersion degree was largely influenced by the filler size. As the filler dimension became smaller, the dispersion parameter D_0.1 largely decreased as quantified, which demonstrated the challenges associated with improving the dispersion of smaller fillers. This work provided a method to quantitatively compare the dispersion degrees of CNF/CNT polymer nanocomposites.     

Porous graphene gels: Preparation and its electrochemical properties

Ultra-light porous 3D network graphene oxide (GO) gels were prepared using a simple process of aqueous gel precursor freezing, solvent exchange, and ethanol drying rather than supercritical drying technology. The GO sheets were consolidated by cross-linked sodium alginate (SA) and the obtained GO–SA gel was reduced by glucose to prepare graphene nanosheet–SA (GN–SA) gel. The gels were characterized by FTIR, XRD, SEM, and nitrogen adsorption–desorption measurements. SA was proven to attach to GO or GN surfaces to form gels composed of macropores and mesopores. GO–SA gel exhibited a bulk density of 16.79 mg cm⁻³, and adsorbed water 17.4 times, ethanol 20.5 times, and soybean oil 22.4 times the weight of GO–SA gel, while GN–SA gel exhibited a lower bulk density of 12.93 mg cm⁻³, and adsorbed water 12.2 times, ethanol 16.9 times and soybean oil 32.3 times the weight of GN–SA gel. The electrochemical performance of the GN–SA gel was analyzed using cyclic voltammetry, electrochemical impedance spectrometry, and chronopotentiometry. The results revealed that GN–SA gel displayed superior capacitive performance with large capacitance (114.12 F g⁻¹) and excellent cyclic performance.     

Shrinking patterns and phase coexistence of polymer gels

We have investigated the shrinking phase transition of slightly ionized poly(N-isopropylacrylamide) (NIPA) gels. The macroscopic conformation change was observed on the heating process in two different methods; a continuous heating process and an isothermal process. It was found that the macroscopic behavior can be characterized by several conformation changes, the phase coexistence (or ‘linked-dumplings’), the grain pattern, the bubble pattern, and the opaque phase. Those have correlations with the phase transition velocity. The heating conditions to determine the characteristic conformations and the stability of the phase coexistence were qualitatively discussed in terms of the classical phase separation model of nucleation and spinodal decomposition.     

Adsorption of proteins on electro-conductive polymer films

Shapable electro-conductive (SEC) polymer films (polyanion-doped polypyrrole films) show several interesting properties for bioelectrochemical applications. The SEC film can be used as an inert, stable and hydrophobic electrode in aqueous solution over a wide potential range. In this study, the physical and the potential-assisted adsorption of various proteins on the SEC film is described. Because of the hydrophobic surface characteristic proteins easily adsorb and retain on the film surface by strong hydrophobic interactions. The amount of the adsorbed protein varies from 2.2 to 4.8 μg cm⁻² depending on the protein when the film is incubated for 22 h in the protein solution. The adsorption is effectively accelerated and enhanced by applying a positive potential in the range from 0.4 V to 1.0 V (vs. Ag/AgCl). The potential-assisted adsorption process is completed by 10–15 min and the amount of the adsorbed protein is nearly doubled as compared to the adsorption without potential. The adsorbed protein is chemically very stable in comparison with the protein in solution. More than 85% of the initial adsorbed proteins retains on the surface after three weeks of incubation in buffer solution. The initial adsorption rate is studied by quartz crystal micro-balance measurements on a thin polymer film coated quartz crystal. In addition, the SEC film surface is etched with air plasma which leads to a four-fold increase of the adsorption of proteins.     

Stimulus-responsive fluidic dispersions of rod shaped liquid crystal polymer colloids

Electrically responsive liquid crystal polymer nanorods were fabricated by template synthesis. Liquid crystal monomers are templated by alumina membranes. Molecular ordering of the liquid crystal molecules resulted from the confinement in the sub-micron channels and this ordering can be captured permanently through photo-polymerization. Template removal and sonication result in individual rods that can be reoriented by applied electrical and magnetic fields. Such anisotropic particles have significant potential applications in electro-rheological fluids and in active mixing in microfluidic channels.     

Integration of copper multilevel interconnects with oxide and polymer interlevel dielectrics

Copper interconnect structures are being evaluated for 0.25 μm minimum feature size technology and below. This work focuses on fabrication of one- and two-level test structures with copper metallization and both oxide and polymer interlevel dielectrics to demonstrate the compatibility of unit processes being developed for future copper-based interconnects. Emphasis is placed on dual Damascene patterning and material and process compatibility with such patterning and the required barriers and passivation techniques required with copper. Future directions of this work are described in this invited review paper.     

Development and characterization of thin polymer films relevant to fiber processing

Dilute solutions of cellulose, polypropylene, polyethylene, nylon and polyester were spun cast onto gold and silica wafers to generate thin films of these polymers, which are commonly used in the manufacture of synthetic fibers. The thin films were used as substrates in the quartz crystal microbalance and nano-indentation techniques to monitor adsorption and friction behaviors after treatment with a polymer solution (as a mimic of a textile finish). The spin coating conditions were optimized in terms of the resulting film morphology, thickness and surface energy. Atomic force microscopy, X-ray photoelectron spectrometry, ellipsometry and contact angle were used to probe the physical and surface properties of the resulting films. Overall, we developed thin films that are helpful to inquire, at the molecular level, phenomena relevant to fiber and textile processing including swelling, degradation, and adsorption of polymers and surfactants.     

Hybrid photovoltaic devices of polymer and ZnO nanofiber composites

Organic semiconductor-based photovoltaic devices offer the promise of a low-cost photovoltaic technology that could be manufactured via large-scale, roll-to-roll printing techniques. Existing organic photovoltaic devices have currently achieved solar power conversion efficiencies greater than 3%. Although encouraging, the reasons higher efficiencies have not been achieved are poor overlap between the absorption spectrum of the organic chromophores and the solar spectrum, non-ideal band alignment between the donor and acceptor species, and low charge carrier mobilities resulting from the disordered nature of organic semiconductors. To address the latter issues, we are investigating the development of nanostructured oxide/conjugated polymer composite photovoltaic (PV) devices. These composites can take advantage of the high electron mobilities attainable in oxide semiconductors and can be fabricated using low-temperature solution-based growth techniques. Additionally, the morphology of the composite can be controlled in a systematic way through control of the nanostructured oxide growth. ZnO nanostructures that are vertically aligned with respect to the substrate have been grown. Here we discuss the fabrication of such nanostructures and present results from ZnO nanofiber/poly(3-hexylthiophene) (P3HT) composite PV devices. The best performance with this cell structure produced an open circuit voltage (V_oc) of 440 mV, a short circuit current density (J_sc) of 2.2 mA/cm², a fill factor (FF) of 0.56, and a conversion efficiency (η) of 0.53%. Incorporation of a blend of P3HT and (6,6)-phenyl C₆₁ butyric acid methyl ester (PCBM) into the ZnO nanofibers produced enhanced performance with a V_oc of 475 mV, J_sc of 10.0 mA/cm², FF of 0.43, and η of 2.03%. The power efficiency is limited in these devices by the large fiber spacing and the reduced V_oc.     

Phase separation and surface morphology of spin-coated films of polyetherimide/polycaprolactone immiscible polymer blends

The surface morphology in thin films of immiscible polyetherimide and polycaprolactone blends was studied using scanning electron and atomic force microscopy. The thin films were obtained by spin-coating from dichloromethane solution. A self-assembled periodic pattern of phase separated domains was observed, which was induced by capillary effects along with the solution radial flow and the unsteady air flow field above the film during the initial stages of spin-coating. A secondary phase separation was observed during the solvent evaporation stage of spin-coating. The differences in surface topographies of the two distinct phases are attributed to different solvent evaporation rates within each phase. In addition, a great variety of domain structures and surface morphologies were observed as a function of polymer blend composition.     

Swelling-induced delamination causes folding of surface-tethered polymer gels

When a polymer film that is weakly attached to a rigid substrate is exposed to solvent, swelling-induced compressive stress nucleates buckle delamination of the film from the substrate. Surprisingly, the buckles do not have a sinusoidal profile, instead, the film near the delamination buckles slides toward the buckles causing growth of sharp folds of high aspect ratio. These folds do not result from a wrinkle-to-fold transition; instead, the film goes directly from a flat state to a folded state. The folds persist even after the solvent evaporates. We propose that patterned delamination and folding may be exploited to realize high-aspect ratio topological features on surfaces through control of a set of boundary constraints arising from the interrelation of film-surface adhesion, film thickness and degree of swellabilty.     

Matrix-assisted pulsed laser deposition of polymer and nanoparticle films

Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique was used to deposit films of Poly(9,9-dioctylfluorene) - PFO and Methoxy Ge Triphenylcorrole [Ge(TPC)OCH3]. The PFO was dissolved in different matrices, like chloroform-CHCl3, tetrahydrofuran - THF and toluene with a 0.5 wt % concentration, while Ge(TPC)OCH3 was diluted in THF with a concentration of 0.01 wt %. The frozen targets were irradiated with a KrF excimer laser. The, films presented good emission properties to be exploited in light emitting devices and gas sensors based on luminescence quenching. The working principle of the MAPLE technique was used for the deposition of colloidal nanoparticles and nanorods, too. TiO2 colloidal nanoparticles (diameter: ∼10 nm) and nanorods (diameter: 5 nm; length: 50 nm) were diluted in deionised water (0.02 wt %) and toluene (0.016 wt %) respectively. The deposited nanostructures preserved dimensions and structural properties of the starting particles and the films showed very interesting electrical responses when exposed to oxidizing gases for sensing applications.     

Improved power conversion efficiency of dye-sensitized solar cells using side chain liquid crystal polymer embedded in polymer electrolytes

Side chain liquid crystal polymer (SCLCP) embedded in poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based polymer electrolytes (PVdF-co-HFP:side chain liquid crystal polymer (SCLCP)) was prepared for dye-sensitized solar cell (DSSC) application. The polymer electrolytes contained tetrabutylammonium iodide (TBAI), iodine (I₂), and 8 wt% PVdF-co-HFP in acetonitrile. DSSCs comprised of PVdF-co-HFP:SCLCP-based polymer electrolytes displayed enhanced redox couple reduction and reduced charge recombination in comparison to those of the conventional PVdF-co-HFP-based polymer electrolyte. The significantly increased short-circuit current density (J_sc, 10.75 mA cm⁻²) of the DSSCs with PVdF-co-HFP:SCLCP-based polymer electrolytes afforded a high power conversion efficiency (PCE) of 5.32% and a fill factor (FF) of 0.64 under standard light intensity of 100 mW cm⁻² irradiation of AM 1.5 sunlight.     

Design,preparation, and application of ordered porous polymer materials

Ordered porous polymer (OPP) materials have extensively application prospects in the field of separation and purification, biomembrane, solid supports for sensors catalysts, scaffolds for tissue engineering, photonic band gap materials owing to ordered pore arrays, uniform and tunable pore size, high specific surface area, great adsorption capacity, and light weight. The present paper reviewed the preparation techniques of OPP materials like breath figures, hard template, and soft template. Finally, the applications of OPP materials in the field of separation, sensors, and biomedicine are introduced, respectively.     

Rheological and textural properties of microemulsion-based polymer gels with indomethacin

Abstract

In this paper, we present novel microemulsion (ME)-based semisolid polymer gels designed for topical administration of poorly water soluble non-steroidal anti-inflammatory drugs. Indomethacin (IND) was used as a model compound. The ME consisted of castor oil, water, Tween®80 as a surfactant and ethanol as cosurfactant. To obtain the desired consistency of the formulations Carbopol®960 was applied as a thickening agent. The aim of the study was to analyze in detail the mechanical properties of the obtained systems, with special attention paid to the features crucial for topical application. The rheological and textural experiments performed for samples with and without the incorporated drug clearly indicate that flow characteristics, viscoelastic properties and texture profiles were affected by the presence of IND. Novel semisolid formulations with IND described for the first time in this paper can be considered as an alternative for commercially available conventional topical dosage forms.     

Sound absorption behavior of multiporous hollow polymer micro-spheres

Multiporous polymer micro-spheres with interconnected cavities have been prepared by a simple modified emulsion polymerization of acrylate monomers and polymerizable emulsifier. The morphology of micro-spheres was characterized by a scanning electron micrographs (SEM) and the sound absorption behavior of the micro-spheres materials was tested in an impedance tube. It is shown that the porous structures and low density allow the micro-spheres to embrace more diversified modes to attenuate sound wave energy. Besides the sound energy being dissipated at the interface of the air and the solid structures of micro-spheres, high absorption coefficient are given rise to by the vibration of the micro-spheres at the resonant frequencies.     

Self-repairing property of polymer network with dangling chains

A new type of self-repairing polymer was proposed by utilizing strong topological interaction of dangling chains in the network polymer that was obtained by eliminating sol-fraction in a weak gel just beyond sol-gel transition point. It was confirmed that an applied cleavage by a razor blade was healed at room temperature without any manual intervention.