Ion exchange, anisotropic structure and thermal stability of polypyrrole films

The thermal stability of electrochemically prepared polypyrrole (PPy) films with p-toluene sulfonate (pTS) or perchlorate (CIOP₄⁻) counter ion (PPy/pTS and PPy/ClO₄⁻) is improved by simple treatment with aqueous sulfuric acid, sodium sulfate or sodium bisulfate. The degree of stabilization achieved depends on the solution, temperature and duration of treatment. PPy/pTS is easily stabilized and thick films (43μm) retain 90 % of the initial conductivity after long period (300 h) at 150 °C, while thinner films (12 μm) retain slightly less (70 %). A model for the conductivity decay has been proposed. Although the mechanism for improved stability is not yet clear it is apparent that the level of ion exchange and the original polymer microstructure are important. The early stages of ion exchange are not symmetrical and diffusion is facilitated at the electrode side of the film. Furthermore, X-ray diffraction shows no evidence of morphological change after treatment of thick PPy/pTS but in thin PPy/pTS and PPy/ClO₄⁻ films an additional peak is indicative of more ordered structure following treatment. These observation may imply that there is a higher density of crosslinks and branching at the growth side than at the electrode side of the film.

Flux-assisted self-assembly of monodisperse colloids

We have developed a novel method to grow ordered layers of monodisperse colloids on a flat substrate. The evaporation of the colloidal suspension in the presence of the inclined substrate is strengthened by an external gas flux directed on the meniscus. The meniscus oscillations caused by the gas flux have an evident effect on the ordering of the spheres on the substrate. Thick films (more than 150 layers in a single-step deposition) of large area single crystals (1 cm2) can be obtained in a very short time (~1 cm/h maximum growth rate) and from very diluted suspensions (up to 0.022% volume fraction).

Inverse opal nanoassemblies : novel architectures for gas sensors the SnO2:Zn case

A novel technique is here presented, based on inverse opal metal oxide structures for the production of high quality macro and meso-porous structures for gas sensing. Taking advantage of a sol-gel templated approach. different mixed semiconducting oxides with high surface area, commonly used in chemical sensing application, were synthesized. In this work we report the
comparison between SnO₂ and SnO₂:Zn. As witnessed by Scanning and Transmission Electron Microscopy (SEM and TEM) analyses and by Powder x-ray Diffraction (PX RD), highly ordered meso-porous structures were formed with oxide crystalline size never exceeding 20 nm . The filled templates. in form of thick films, were bound to allumina substrate with Pt interdigitated contacts
and Pt heater, through in situ calcination, in order to perform standard electrical characterization. Pollutant gases like CO and NO₂ and methanol. as interfering gas, were used for the targeted electrical gas tests. All samples showed low detection limits towards both reducing and oxidizing species in low temperature measurements. Moreover, the addition of high molar percentages of Zn( II) affected the beha viour of electrical response improv ing the se lecti vity of the proposed system.

Dynamics of interactions involving deformable drops : hydrodynamic dimpling under attractive and repulsive electrical double layer interactions

A model developed previously to analyze force measurements between two deformable droplets in the atomic force microscope [Langmuir 2005, 21, 2912-2922] is used to model the drainage of an aqueous film between a mica plate and a deformable mercury drop for both repulsive and attractive electrical double-layer interactions between the mica and the mercury. The predictions of the model are compared with previously published data [Faraday Discuss. 2003, 123, 193-206] on the evolution of the aqueous film whose thickness has been measured with subnanometer precision. Excellent agreement is found between theoretical results and experimental data. This supports the assumptions made in the model which include no-slip boundary conditions at both interfaces. Furthermore, the successful fit attests to the utility of the model as a tool to explore details of the drainage mechanisms of nanometer-thick films in which fluid flow, surface deformations, and colloidal forces are all involved. One interesting result is that the model can predict the time at which the aqueous film collapses when attractive mica-mercury forces are present without the need to invoke capillary waves or other local instabilities of the mercury/electrolyte interface.

Electromagnetic interference shielding and radiation absorption in thin polypyrrole films

Results of permittivity measurements, electromagnetic interference shielding effectiveness, and heat generation due to microwave absorption in conducting polymer coated textiles are reported and discussed. The intrinsically conducting polymer, polypyrrole, doped with anthraquinone-2-sulfonic acid (AQSA) or para-toluene-2-sulfonic acid (pTSA) was applied on textile substrates and the resulting materials were investigated in the frequency range 1–18 GHz. The 0.54 mm thick conducting textile/polypyrrole composites absorbed up to 49.5% of the incident 30–35 W microwave radiation. A thermography station was used to monitor the temperature of these composites during the irradiation process, where absorption was confirmed via visible heat losses. Samples with lower conductivity showed larger temperature increases caused by microwave absorption compared to samples with higher conductivity. A sample with an average sheet resistivity of 150 Ω/sq. showed a maximum temperature increase of 5.27 °C, whilst a sample with a lower resistivity (105 Ω/sq.) rose by 3.85 °C.

Surface-Enhanced Infrared Spectra of Manganese (III) Tetraphenylporphine Chloride Physisorbed on Gold Island Films

Surface-enhanced infrared absorption (SEIRA) spectra of manganese (III) tetraphenylporphine chloride (Mn(TPP)Cl) on metal island films were measured in transmission mode. Dependences of the enhancement factor of SEIRA on both the sample quantity and the type of evaporated metal were investigated by subsequently increasing the amount of Mn(TPP)Cl on gold and silver substrates. The enhancement increases nonlinearly with the amount of sample and varies slightly with the thickness of metal islands. In particular, the SEIRA transmission method presents an anomalous spectral enhancement by a factor of 579, with substantial spectral shifts, observed only for the physisorbed Mn(TPP)Cl that remained on a 3-nm-thick gold film after immersion of the substrates into acetone. A charge-transfer (CT) interaction between the porphyrinic Mn and gold islands is therefore proposed as an additional factor in the SEIRA mechanism of the porphyrin system. The number of remaining porphyrin molecules was estimated by calibration-based fluorescence spectroscopy to be 2.36×1013 molecules (i.e., ~2.910-11 mol/cm2) for a 3-nm-thick gold film, suggesting that the physisorbed molecules distributed very loosely on the metal island surface as a result of the weak van der Waals interactions. Fluorescence microscopy revealed the formation of microcrystalline porphyrin aggregates during the consecutive increase in sample solution. However, the immersion likely redistributed the porphyrin to be directly attached on the gold surface, as evidenced by an absence of porphyrinic microcrystals and the observed SEIRA enhancement. The distinctive red shift in the UV-visible spectra and the SEIRA-enhanced peaks indicate the presence of a preferred orientation in the form of the porphyrin ring inclined with respect to the gold surface.

Symmetrically tapered <30-micron-thick quasi-planar Ge waveguides as chemical sensors for microanalysis

Symmetrically tapered planar IR waveguides have been fabricated by starting with a ZnS coated concave piece of single-crystal Ge, embedding it in an epoxide resin as a supporting substrate, and then grinding and polishing a planar surface until the thickness at the taper minimum is <30 μm. Such tapering is expected to enhance a waveguide's sensitivity as an evanescent wave sensor by maximizing the amount of evanescent wave energy present at the thinnest part of the waveguide. As predicted by theory, the surface sensitivity, i.e., the absorbance signal per molecule in contact with the sensing region, increases with decreasing thickness of the tapered region even while the total energy throughput decreases. The signal-to-noise ratio obtained depends very strongly on the quality of the polished surfaces of the waveguides. The surface sensitivity is superior to that obtained with a commercial Ge attenuated total reflection (ATR) accessory for several types of sample, including thin films (<10 ng) and small volumes (<1 μL) of volatile solvents. By using the waveguides, light-induced structural changes in the protein bacteriorhodopsin were observable using samples as small as ∼50 pmol (∼1 μg). In addition, the waveguide sensors can reveal the surface compositions on a single human hair, pointing to their promise as a tool for forensic fiber analysis.

Stability of aqueous films between bubbles. Part 1. The effect of speed on bubble coalescence in purified water and simple electrolyte solutions

Film thinning experiments have been conducted with aqueous films between two air phases in a thin film pressure balance. The films are free of added surfactant but simple NaCl electrolyte is added in some experiments. Initially the experiments begin with a comparatively large volume of water in a cylindrical capillary tube a few millimeters in diameter, and by withdrawing water from the center of the tube the two bounding menisci are drawn together at a prescribed rate. Thismodels two air bubbles approaching at a controlled speed. In pure water, the results show three regimes of behavior depending on the approach speed; at slow speed (<1 μm/s) it is possible to form a flat film of pure water, ∼100 nm thick, that is stabilized indefinitely by disjoining pressure due to repulsive double-layer interactions between naturally charged air/water interfaces. The data are consistent with a surface potential of -57mV on the bubble surfaces. At intermediate approach speed (∼1-150 μm/s), the films are transiently stable due to hydrodynamic drainage effects, and bubble coalescence is delayed by ∼10-100 s. At approach speeds greater than ∼150 μm/s, the hydrodynamic resistance appears to become negligible, and the bubbles coalesce without any measurable delay. Explanations for these observations are presented that take into account Derjaguin-Landau-Verwey-Overbeek and Marangoni effects entering through disjoining pressure, surface mobility, and hydrodynamic flow regimes in thin film drainage. In particular, it is argued that the dramatic reduction in hydrodynamic resistance is a transition from viscosity-controlled drainage to inertia-controlled drainage associated with a change from immobile to mobile air/water interfaces on increasing the speed of approach of two bubbles. A simple model is developed that accounts for the boundaries between different film stability or coalescence regimes. Predictions of the model are consistent with the data, and the effects of adding electrolyte can be explained. In particular, addition of electrolyte at high concentration inhibits the near-instantaneous coalescence phenomenon, thereby contributing to increased foam film stability at high approach speeds, as reported in previous literature. This work highlights the significance of bubble approach speed as well as electrolyte concentration in affecting bubble coalescence.

Crosslinking neat ultrathin films and nanofibres of pH-responsive poly(acrylic acid) by UV radiation

Electrospun polyelectrolyte hydrogel nanofibres are being developed for many applications including artificial muscles, scaffolds for tissue engineering, wound dressings and controlled drug release. For electrospun polyelectrolytes, a post-spinning crosslinking process is necessary for producing a hydrogel. Typically, radiation or thermal crosslinking routines are employed that require multifunctional crosslinking molecules and crosslink reaction initiators (free radical producers). Here, ultraviolet subtype-C (UVC) radiation was employed to crosslink neat poly(acrylic acid) (PAA) nanofibres and films to different crosslink densities. Specific crosslink initiators or crosslinking molecules are not necessary in this fast and simple process providing an advantage for biological applications. Scanning probe microscopy was used for the first time to measure the dry and wet dimensions of hydrogel nanofibres. The diameters of the swollen fibres decrease monotonically with increasing UVC radiation time. The fibres could be reversibly swollen/contracted by treatment with solutions of varying pH, demonstrating their potential as artificial muscles. The surprising success of UVC radiation exposure to achieve chemical crosslinks without a specific initiator molecule exploits the ultrathin dimensions of the PAA samples and will not work with relatively thick samples.