Solvent-induced intramolecular exciplex fluorescence of β-naphthylmethyl amine

Intramolecular exciplex fluorescence of β-naphthylmethyl amine has been observed in polar media. The absence of exciplex fluorescence and the quenching of naphthalene-type fluorescence in hydrocarbon solvents is explained in terms of enhanced intersystem crossing. The crucial role the solvent can play in determining the energy and intensity of exciplex fluorescence is clearly demonstrated.     

Vapor deposition of ultrathin hydrophilic polymer coatings enabling candle soot composite for highly sensitive humidity sensors

Candle soot (CS) is a desirable carbon nanomaterial for sensors owing to its highly porous nanostructure and large specific surface area. CS is advantageous in its low-cost and facile preparation compared to graphene and carbon nanotubes, but its pristine nanostructure is susceptible to collapse, hampering its application in electronic devices. This article reports conformal coating of nanoscale crosslinked hydrophilic polymer on CS film using initiated chemical vapor deposition, which well preserved the CS nanostructure and obtained nanoporous CS@polymer composites. Tuning coating thickness enabled composites with different morphologies and specific surface areas. Surprisingly, the humidity sensor made from composite with the lowest filling degree, thus largest specific surface area, showed relatively low sensitivity, which is likely due to its discontinuous structure, thus insufficient conductive channels. Composite sensor with optimum filling degree shows excellent sensing response of more than 10³ with the linearity of R² = 0.9400 within a broad relative humidity range from 11% to 96%. The composite sensor also exhibits outstanding sensing performance compared to literature with low hysteresis (3.00%), a satisfactory response time (28.69 s), and a fast recovery time (0.19 s). The composite sensor is fairly stable and durable even after 24 h soaking in water. Furthermore, embedding a humidity sensor into a face mask realizes real-time monitoring of human breath and cough, suggesting promising applications in respiratory monitoring.     

Entanglement of polymer chains in ultrathin films

This investigation aimed to clarify the issue of whether polymer chains are entangled in ultrathin films spin-coated onto substrates. This was done using a fluorescence probe method to observe the behavior of two types of poly(methyl methacrylate) (PMMA), one having a carbazolyl (Cz) moiety (PMMA-Cz) and the other having an anthryl (At) moiety (PMMA-At). In both cases, the moiety fraction was 1 unit for 400 units of polymer. We prepared ultrathin films (thickness: 4-88 nm) on quartz substrates from PMMA-Cz, PMMA-At, and a mixture of the two using a spin-coating method. When the PMMA films prepared from the mixture of the two PMMAs were excited at 292 nm, which is preferentially absorbed by Cz rather than At, the Cz fluorescence was found to be quenched dramatically while the At fluorescence increased significantly. This effect is due to the proximity of the Cz to the At, which permits the transfer of excitation energy between them. The average distance between Cz and At can be calculated using the F?rster mechanism. When the ultrathin film thickness was between 12 and 88 nm, the average distance was found to be 2 nm. This is much shorter than the radii of gyration of the polymers. From this it is clear that two polymer molecules in an ultrathin film do experience entanglement, as has been hypothesized. Thus, we conclude that the difference between certain properties of ultrathin films and the properties of the same materials in bulk are not induced by a decrease in the level of polymer chain entanglement.     

Positron implantation in polymer coatings

The implantation of positrons from a²²Na source has been studied in two polymer coatings. Transmitted intensities, effective mass absorption coefficients and implantation profiles have been determined.     

Electrochemical properties of PP membranes with plasma polymer coatings of acrylic acid

Commercial polypropylene (PP) membranes were modified by plasma polymerization coating of acrylic acid, in combination with oxygen flow or oxygen plasma etching. First, conditions for plasma polymerization coating were optimized in terms of the chemical resistance of the coatings and their ion exchange capacity as a function of plasma power, internal pressure and treatment time. Next, the plasma polymerization coating of acrylic acid was combined with oxygen flow or oxygen plasma etching, and their conditions were also optimized by measuring the ion exchange capacity. Finally, the modified membranes were subjected to electrical resistance and transport number measurements and characterized by -step, FT-IR/ATR and SEM. Among the modification methods, oxygen plasma etching followed by the plasma polymerization coating of acrylic acid provided the best electrochemical properties with 1.75 meq/g (IEC) and 112 Ω cm² (ER), 0.88 (TN).     

Effect of precipitants on polymer film porosity

IR spectroscopy and electron microscopy have been employed to study the effect of precipitants on the formation of porous structures in poly(vinyl alcohol)-based and modified polyacrylonitrile-based polymer films prepared by the wet casting method. Conditions for formation of porous structures in the polymer films are established as depending on parameters of solubility and pH of precipitants. The spectral method is tested for studying porosity of polymer materials in near and medium IR regions.     

Synthesis of ultrathin polymer films by self assembly

Recent progresses in the self assembly of ultrathin polymer films are described. Bilayer membranes of polymeric hydrogen-bond networks are formed in water. Two-dimensional networks of organic and inorganic polymers are formed in cast films of synthetic bilayer membranes to give stable multilayer films upon removal of the matrices. The monolayer at the air-water interface constitutes suitable templates for 2D polymer networks, and it may be either removed or part of the 2D film. Successive adsorption of polycations and polyanions under carefully controlled conditions produces layered polyion complexes in the stepwise manner. Various polymer chains are epitaxially adsorbed onto graphite. All these results indicate that molecularly defined 2D polymer structures are readily available.     

Surface instabilities in ultrathin, cross-linked poly(N-isopropylacrylamide) coatings

Near-the-surface instabilities with a cusplike morphology were observed in ultrathin photo-cross-linked poly(N-isopropylacrylamide) coatings upon swelling in water. The characteristic wavelength of the instability was approximately 25 times the dry thickness and scaled linearly with coating thickness between 30 and 1200 nm. Above 1200 nm, slippage of the coating along the confining substrate led to reticulated patterns with a much larger wavelength. To help interpret the origin of the instability, the coatings were also exposed to a solvent slightly worse than water (acetone) and a solvent slightly better than water (isopropanol). In all cases, the characteristic wavelength scaled linearly with respect to the swelling induced by each solvent. Both water and isopropanol produced well-defined cusps or folds in the gel surface, while acetone produced semiordered blisters that grew into one another. The features produced in acetone may be a consequence of swelling being close to the threshold value for the loss of planar stability. Through the use of a first-order linear perturbation of the Flory-Rehner model, it is shown that the emergence of a characteristic wavelength is consistent with an inhomogeneous distribution of solvent that results from diffusion of solvent into a dry coating.     

Nanostructured ultraviolet resistant polymer coatings

Nanoparticle-embedded acrylic coatings that can absorb copious amounts of UV radiation yet scatter little were developed to protect base fabrics from sun-induced degradation. Zinc oxide and titanium dioxide nanoparticles with diameters ranging from 15 to 70 nm were used. Nanoparticles (5 wt%) were dispersed in acrylic emulsions. Nanoparticle-embedded acrylic films of 10 μm and 20 μm thick were prepared and bonded to Kevlar fabric. Mechanical tests as well as infrared, visible and UV spectroscopy were used to characterize nanoparticle-embedded acrylic emulsions and coated Kevlar fabric.The changes in mechanical and chemical properties of Kevlar fabric after a day and week of intense UV exposure were assessed using tear and strip tensile testing, UV, visible and infrared spectroscopy, and wide and small angle X-ray analysis. Tear and tensile data, with support from UV results, showed that 20 μm nanoparticle-embedded coatings largely prevented degradation of Kevlar fabric, allowing only 5% of the degradation that occurred in the unprotected fabric after a week of UV exposure.     

Fluorescent quantum yield of pyrene probe in ultrathin polymer films

The fluorescently labelled polymers including pyrene-labelled polystyrene (PyPS) and pyrene-labelled poly(methyl methacrylate) (PyPMMA) with narrow molecular weight distributions were synthesized by the atom transfer radical copolymerization (ATRCP) of styrene or methyl methacrylate with 1-pyrenemethyl methacrylate (PyMMA). The ultrathin PyPS and PyPMMA films with the thickness ranging from 30 nm to 400 nm supported on the quartz slides were prepared by spin-coating. The fluorescent quantum yield (QY) of the pyrene probe in the ultrathin polymer films was investigated by the photoluminescence spectrometer using an integrating sphere detector. The QY decreased with the reduction of film thickness in the sub-200 nm range.     

Assembly of ultrathin polymer multilayer films by click chemistry

Layer-by-layer (LbL) assembly is a versatile and robust technique for fabricating tailored thin films of diverse composition. Herein we report a new method of covalent coupling, click chemistry, to facilitate the LbL assembly of thin films. Linear film growth was observed using both UV-vis and FTIR spectroscopy, and film thicknesses were determined by ellipsometry and atomic force microscopy. The assembled films are shown to be stable in a wide pH range. This technique offers the potential to enable the synthesis of new types of stable and responsive LbL films from a variety of polymers.     

Models for cracking of polymer coatings

We investigate the dynamics of cracking of a brittle coating covering an elastically stretched substrate. We consider here a scalar model (an electrical analogue) in order to describe fractures in thin and in thick films. The model captures the essential features of the fragmentation of coatings and allows us to classify different temporal regimes in the cracking process and to obtain several basic patterns of the cracks' morphology.     

Dispersion and phase separation of carbon nanotubes in ultrathin polymer films

The inner structure and nanoscale distribution of the stiffness was studied for polymer-single-wall carbon nanotube composites. Dispersion of nanotubes in a polystyrene and polyurethane polymer matrix was achieved by a proper choice of the organic solvent (NMP) and sonification of polymer/SWNT solutions. Ultrathin nanocomposite films were prepared through a dip-coating procedure and possessed a noticeable degree of nanotube orientation in the direction of the applied shear force. Peculiarities of the phase separation in the films were studied by atomic force microscopy (with application of force modulation mode to map the nanotube distribution within the polymer matrix) and Raman spectroscopy.     

Interfacial glass transition profiles in ultrathin, spin cast polymer films

Interfacial glass transition temperature (T(g)) profiles in spin cast, ultrathin films of polystyrene and derivatives were investigated using shear-modulated scanning force microscopy. The transitions were measured as a function of film thickness (delta), molecular weight, and crosslinking density. The T(g)(delta) profiles were nonmonotonic and exhibited two regimes: (a) a sublayer extending about 10 nm from the substrate, with T(g) values lowered up to approximately 10 degrees C below the bulk value, and (b) an intermediate regime extending over 200 nm beyond the sublayer, with T(g) values exceeding the bulk value by up to 10 degrees C. Increasing the molecular weight was found to shift the T(g)(delta) profiles further from the substrate interface, on the order of 10 nm/kDa. Crosslinking the precast films elevated the absolute T(g) values, but had no effect on the spatial length scale of the T(g)(delta) profiles. These results are explained in the context of film preparation history and its influence on molecular mobility. Specifically, the observed rheological anisotropy is interpreted based on the combined effects of shear-induced structuring and thermally activated interdiffusion.     

Adhesive bonding of glassy polymer surfaces by an ultrathin layer of a semicrystalline polymer

To develop a greater understanding of interfacial interactions between a semicrystalline polymer and a glassy polymer, adhesion tests were performed on very thin layers of poly(ethylene oxide) (PEO) sandwiched between two layers of poly(tetramethyl bisphenol A polycarbonate) (TMPC). The tests were designed to provide intimate contact between the surfaces while they were heated above the melting point of the PEO and cooled back to room temperature. A contact mechanics approach, based on the Johnson, Kendall, and Roberts theory, was used to determine values of the energy release rate describing the energetic driving force for crack propagation within the interfacial region. The ability to measure crack propagation at large values of the energy release rate was limited by rupture of the silicone elastomer that was used to provide a sufficiently compliant matrix for the adhesion experiment. By cycling the tensile stress at relatively low loading levels, we were able to measure fatigue crack propagation at values of the energy release rate that did not result in failure of the elastomer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3809–3821, 2004     

Time-resolved ultrathin cobalt film growth on a colloidal polymer template

Cobalt (Co) sputter deposition onto a colloidal polymer template is investigated using grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). SEM and AFM data picture the sample topography, GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is observed.