Composition depth profiling of polystyrene/poly(vinyl ethyl ether) blend thin films by angle resolved XPS

Angle resolved XPS (ARXPS) and scanning force microscopy (SFM) are used to study polystyrene/poly(vinyl ethyl ether) 50/50 wt% blend thin films spin cast from toluene solution, as a function of polystyrene molecular weight and film thickness. ARXPS is used to investigate the composition depth profile (CDP) of the blend thin films and SFM to study their surface morphology and miscibility. The CDPs are modelled by an empirical hyperbolic tangent function with three floating parameters. These are determined by non-linear least squares regression, their uncertainties estimated and the curve fit residuals analysed to demonstrate that the hyperbolic tangent CDP is a satisfactory fit to the ARXPS data. Conclusions are drawn regarding the behaviour of the blend thin films as the thickness and polystyrene molecular weight are varied. Flory-Huggins interaction parameters (chi) for the mixtures are calculated based upon the segregation data, and suggest a value of chi = 0.05 to be appropriate for this system. (c) 2009 Elsevier B.V. All rights reserved

Application of mean-field theory to the spin casting of polystyrene and poly(methyl methacrylate) blend films from toluene

The Flory-Huggins free energy of mixing is shown to be appropriate for the analysis of the temporal evolution of a ternary blend of polystyrene and poly (methyl methacrylate) during spin-coating from toluene using an in-situ light scattering technique. For the range of concentrations studied, both the onset of film instability and the observation of a scattering ring occur at the same toluene volume fraction. The success of Flory-Huggins theory indicates that polymer chains retain random walk characteristics during spin-coating. It is also concluded that the thermodynamics of phase separation during film formation is independent of the initial solvent concentration

A solution concentration dependent transition from self-stratification to lateral phase separation in spin-cast PS:d-PMMA thin films

Thin films with a rich variety of different nano-scale morphologies have been produced by spin casting solutions of various concentrations of PS:d-PMMA blends from toluene solutions. During the spin casting process specular reflectivity and off-specular scattering data were recorded and ex situ optical and atomic force microscopy, neutron reflectivity and ellipsometry have all been used to characterise the film morphologies. We show that it is possible to selectively control the film morphology by altering the solution concentration used. Low polymer concentration solutions favour the formation of flat in-plane phase-separated bi-layers, with a d-PMMA-rich layer underneath a PS-rich layer. At intermediate concentrations the films formed consist of an in-plane phase-separated bi-layer with an undulating interface and also have some secondary phase-separated pockets rich in d-PMMA in the PS-rich layer and vice versa. Using high concentration solutions results in laterally phase-separated regions with sharp interfaces. As with the intermediate concentrations, secondary phase separation was also observed, especially at the top surface

Dynamics of polymer film formation during spin coating

Standard models explaining the spin coating of polymer solutions generally fail to describe the early stages of film formation, when hydrodynamic forces control the solution behavior. Using in situ light scattering alongside theoretical and semi-empirical models, it is shown that inertial forces (which initially cause a vertical gradient in the radial solvent velocity within the film) play a significant role in the rate of thinning of the solution. The development of thickness as a function of time of a solute-free liquid (toluene) and a blend of polystyrene and poly(methyl methacrylate) cast from toluene were fitted to different models as a function of toluene partial pressure. In the case of the formation of the polymer blend film, a concentration-dependent (Huggins) viscosity formula was used to account for changes in viscosity during spin coating. A semi-empirical model is introduced, which permits calculation of the solvent evaporation rate and the temporal evolution of the solute volume fraction and solution viscosity

Fabrication of arrays of lead zirconate titanate (PZT) nanodots via block copolymer self-assembly

This Article presents a simple methodology for the fabrication of two-dimensional arrays of lead zirconate titanate (PZT) nanodots on n-doped Si substrates via the directed self-assembly of PS-b-PEO block copolymer templates. The approach produces highly ordered PZT nanodot patterns, with lateral widths and heights as small as 20 and 10 nm, respectively, and a coverage density as high as ∼68 × 109 nanodots cm–2. The existence of a perovskite phase in the nanodots was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy. The piezo-amplitude and ferroelectric domain response obtained from the nanodots, through piezoresponse force microscopy, confirmed the presence of ferroelectricity in the PZT arrays. Notably, PZT nanodots with a thickness ∼10 nm, which is close to the critical size limit of PZT, showed ferroelectric behavior. The presence of a multi-a/c domain structure in the nanodots was attributed to their polycrystalline nature

Robust rapid-setting antibacterial liquid bandages

Abstract: Bandaging is a steadfast but time-consuming component of wound care with limited technical advancements to date. Bandages must be changed and infection risk managed. Rapid-set liquid bandages are efficient alternatives but lack durability or inherent infection control. We show here that antibacterial zinc (Zn) and copper (Cu) species greatly enhance the barrier properties of the natural, waterproof, bio-adhesive polymer, shellac. The material demonstrated marked antibacterial contact properties and, in ex-vivo studies, effectively locked-in pre-applied therapeutics. When challenged in vivo with the polybacterial bovine wound infection ‘digital dermatitis’, Zn/Cu-shellac adhered rapidly and robustly over pre-applied antibiotic. The bandage self-degraded, appropriately, over 7 days despite extreme conditions (faecal slurry). Treatment was well-tolerated and clinical improvement was observed in animal mobility. This new class of bandage has promise for challenging topical situations in humans and other animals, especially away from controlled, sterile clinical settings where wounds urgently require protection from environmental and bacterial contamination

Dynamics of polymer film formation during spin coating

\ua9 2014 Author(s).Standard models explaining the spin coating of polymer solutions generally fail to describe the early stages of film formation, when hydrodynamic forces control the solution behavior. Using in situ light scattering alongside theoretical and semi-empirical models, it is shown that inertial forces (which initially cause a vertical gradient in the radial solvent velocity within the film) play a significant role in the rate of thinning of the solution. The development of thickness as a function of time of a solute-free liquid (toluene) and a blend of polystyrene and poly(methyl methacrylate) cast from toluene were fitted to different models as a function of toluene partial pressure. In the case of the formation of the polymer blend film, a concentration-dependent (Huggins) viscosity formula was used to account for changes in viscosity during spin coating. A semi-empirical model is introduced, which permits calculation of the solvent evaporation rate and the temporal evolution of the solute volume fraction and solution viscosity

Quantitative evaluation of evaporation rate during spin-coating of polymer blend films: Control of film structure through defined-atmosphere solvent-casting

Thin films of polymer mixtures made by spin-coating can phase separate in two ways: by forming lateral domains, or by separating into distinct layers. The latter situation (self-stratification or vertical phase separation) could be advantageous in a number of practical applications, such as polymer optoelectronics. We demonstrate that, by controlling the evaporation rate during the spin-coating process, we can obtain either self-stratification or lateral phase separation in the same system, and we relate this to a previously hypothesised mechanism for phase separation during spin-coating in thin films, according to which a transient wetting layer breaks up due to a Marangoni-type instability driven by a concentration gradient of solvent within the drying film. Our results show that rapid evaporation leads to a laterally phase-separated structure, while reducing the evaporation rate suppresses the interfacial instability and leads to a self-stratified final film

Local Thermomechanical Analysis of a Microphase-Separated Thin Lamellar PS‑<i>b</i>‑PEO Film

We use atomic force microscopy (AFM) and hot tip AFM (HT-AFM) to thermophysically characterize a 30 nm thick film of poly­(styrene-<i>block</i>-ethylene oxide), PS-<i>b</i>-PEO, and to modify its lamellar patterns having spacing of 39 ± 3 nm. AFM tip scans of the polymer film induce either abrasive surface patterns or nanoscale ripples, which depend upon the tip force, temperature, and number of scans. The evolution of the lamellar patterns is explained by the polymer film molecular structure and mode I crack propagation in the polymer combined with the stick-and-slip behavior of the AFM tip. The HT-AFM measurements at various tip–sample temperatures and scanning speeds yield several thermophysical quantities: the PEO melting temperature of 54 ± 12 °C, the PS glass transition temperature of 54 ± 12 °C, the PS-<i>b</i>-PEO specific heat of 3.6 ± 2.7 J g^–1 K^–1, the PEO melting enthalpy of 111 ± 88 J g^–1, and the free energy of Helmholtz for PEO unfolding (and melting) of 10^–20 J nm^–2. These quantities are obtained for PS-<i>b</i>-PEO volumes of 30 000 nm³, which correspond to 30 ag of the polymer