Functional coatings for anti-biofouling applications by surface segregation of block copolymer additives

Temperature responsive or bactericidal coatings with poly(n-butyl methacrylate) (PBMA) as bulk material and surface segregated poly(n-butyl acrylate)-block-poly-(N-isopropylacrylamide) (PBA-b-PNIPAAm) or poly(n-butyl acrylate)-block-quaternized poly(2-(dimethylamino)ethyl methacrylate) (PBA-b-PDMAEMAq) as additive were prepared via sequential solvent evaporation of polymer solutions in a solvent mixture. The degree of enrichment at the air surface of the coating and the functionality were examined for different molecular weight additives with different block ratios obtained via Atom Transfer Radical Polymerization (ATRP). The design of the block copolymers with an anchor block (PBA) which is compatible with the bulk polymer (PBMA) and water-compatible functional blocks (PNIPAAm and PDMAEMAq) along with the selection of suited solvent mixtures based on pre-estimation of the selective solubility and sequential evaporation via the Hansen solubility parameters and vapor pressures, respectively, were found to work very well. A small fraction of water in the solvent mixture had been crucial to obtain surface segregation of the functional block, e.g., a PNIPAAm surface with temperature-switchable wettability. Reversible temperature dependent wettability and long term stability of the functionalization, based on contact angle data, were obtained for an optimized PBA-b-PNIPAAm additive. Surface charge density, estimated from dye binding and zeta potential measurements, and killing efficiency against Staphylococcus aureus were investigated for PBA-b-PDMAEMAq as additive. Both block copolymer additives were found to dominate the surface properties and the functionality of the PBMA coating.     

Surface fluctuations of polymer brushes probed by diffuse X-ray scattering

The diffuse scattering from the surfaces of melt and glassy polymer brushes has been studied systematically for the first time using polystyrene (PS) and poly(n-butylacrylate) (PnBA) brushes synthesized by free radical polymerization. The data show unambiguously that the diffuse scattering behavior varies systematically with brush thickness for both types of brushes. We attribute a cross-over in scattering with q_x, the in-plane scattering vector, to the presence of surface thermal fluctuations and their suppression for longer wavelengths, a phenomenon already reported for films of untethered chains. Long wavelength fluctuations are suppressed more strongly on the surface of a PS brush than on the surface of a film of untethered (‘free’) PS chains of comparable thickness, so that even in films of thickness, d, such that d/R_g>5 clear evidence of the suppression of fluctuations can still be seen in the experimentally available range of q_x. Fluctuations are suppressed for q_x less than a lower wavevector cut-off, q_l,c, which changes with film thickness, though much more weakly than for films of free chains. For values of d/R_g<4, where R_g is the unperturbed radius of gyration of a comparable free chain, q_l,c drops as d increases. For d/R_g>4 q_l,c begins to increase with brush thickness, in qualitative agreement with theory, indicative of a transition to a true ‘brush’ state in which stretching of the chains makes longer wavelength fluctuations at the surface unfavorable. Measurements with PnBA brushes having T_g substantially below room temperature confirm the trends mentioned above. Further, they give evidence that the value of q_l,c is temperature insensitive above T_g.     

Grafting of hyperbranched polymers: From unusual complex polymer topologies to multivalent surface functionalization

In this feature article, the grafting of hyperbranched polymers to different substrates is reviewed. Both grafting onto macromolecules with different topologies (homogeneous grafting) and the resulting complex polymer architectures containing highly branched segments as well as their applications are discussed. In the second part grafting of hyperbranched polymers on surfaces, i.e., planar surfaces and spherical particles (heterogeneous grafting), with respect to specific applications, such as bio-repellent surfaces or soluble carbon nanotubes is described. In all cases, the one-step synthesis and the resulting highly branched topology of the hyperbranched building blocks is beneficial for the convenient introduction of a large number of functional groups to the substrates. These multifunctional hybrid materials open interesting options for applications, e.g., for highly functional nanoparticles or nanocomposites.     

Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Multicomponent diffusion of solvents in polymeric systems is not completely understood, despite many scientific contributions to the topic. Literature scarcely offers measurement data on diffusion for model validation in such systems. In this work, the ternary systems consisting of poly(vinyl acetate) and the solvents toluene and methanol was investigated experimentally and numerically. By means of inverse micro Raman spectroscopy (IMRS) concentration gradients in drying thin films have been measured. Initial composition of the samples has been varied systematically in order to detect mutual influence of the solvents' diffusive behavior. It was shown that the mobility of the different species is increased in the presence of other solvents as predicted by theory. This experimental data is provided for model validation. A new expression to calculate the diffusion coefficients in ternary mixtures is proposed which only requires binary data. This expression is tested by means of a model‐based simulation to predict the drying of ternary polymer solutions in terms of concentration profiles and residual solvent content. The results are in very good agreement with the experiments. Cross terms diffusion coefficients and thermodynamic factors were not found to be necessary for a satisfying prediction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43899.     

In situ sol–gel synthesis of tungsten trioxide networks in polymer electrolyte: Dual-functional solid state chromogenic smart film

The novel electro-photochromic solid electrolyte films were successfully synthesized by in situ sol–gel synthesis of tungsten trioxide (WO₃) working electrode within gelatin/lithium cosolvent system. The transparent free-standing single-layer film with adhesiveness and flexibility, darken significantly under the UV radiation with photo-response time of 30 s and gradually reversed once the source of UV was blocked. Moreover, casted film on the indium tin oxide (ITO) glass showed electrochromic (EC) behavior as well in presence of ion storage counter electrode. X-ray diffraction analysis indicates the amorphous nature of an in situ synthesized gelatin-based film. The prepared film containing 30 wt% LiClO₄ and 10 wt% WO₃ (sample designated as GLi30W10) shows ionic conductivity value of 1.1 × 10⁻⁴ S/cm. The EC performances of the device with the following configuration; ITO/GLi30W10/NiO/ITO, was investigated by means of UV and cyclic voltammograms. Good performances and fast electro-response times (2 s/1 s) of the device were demonstrated with coloration efficiency of 51.54 cm²/C.     

The Prato reaction on nanodiamond: Surface functionalization by formation of pyrrolidine rings

The Prato reaction is a highly valued reaction for the functionalization of fullerenes and carbon nanotubes. It uses the generation of pyrrolidine rings from azomethine ylides in the formation of a covalent grafting of functional moieties. Here we present the first application of this reaction on thermally annealed nanodiamond as a way for the grafting of a multitude of functional moieties. We used two types of azomethine ylides (aliphatic and pyridine derived) to show the broad applicability of the reaction for the surface modification of nanodiamond. The possibility to attach glycol units or alkyl chains, both with or without reactive terminal groups opens the way to tune the surface properties of such “Prato-functionalized” diamond in a very flexible way.     

Monte Carlo simulations of phase separation in thin polymer blend films: scaling properties of morphological measures

Surface directed phase separation in thin polymer blend film has been studied with Monte Carlo simulations using a simple model based on reptation method. Time evolution of phase structure was characterized quantitatively by morphological measures (the Minkowski functionals) in addition to the inspection of concentration versus depth profiles. It was shown that the dynamical scaling hypothesis holds for the Minkowski functionals describing morphologies at the early stages of phase separation in thin films. Two time regimes with different scaling exponents (0.25, 0.33) were found for the growth of the characteristic length scale in the system corresponding to various transport mechanisms (diffusion along- and normally to the interface). Fast decrease in the morphological measures observed at the end of phase separation was attributed to the confinement of the thin film.     

Surface modification of linear low‐density polyethylene film by amphiphilic graft copolymers based on poly(higher α‐olefin)‐graft‐poly(ethylene glycol)

In this article, a series of amphiphilic graft copolymers, namely poly(higher α‐olefin‐co‐para‐methylstyrene)‐graft‐poly(ethylene glycol), and poly(higher α‐olefin‐co‐acrylic acid)‐graft‐poly(ethylene glycol) was used as modifying agent to increase the wettability of the surface of linear low‐density polyethylene (LLDPE) film. The wettability of the surface of LLDPE film could be increased effectively by spin coating of the amphiphilic graft copolymers onto the surface of LLDPE film. The higher the content of poly(ethylene glycol) (PEG) segments, the lower the water contact angle was. The water contact angle of modified LLDPE films was reduced as low as 25°. However, the adhesion between the amphiphilic graft copolymer and LLDPE film was poor. To solve this problem, the modified LLDPE films coated by the amphiphilic graft copolymers were annealed at 110° for 12 h. During the period of annealing, heating made polymer chain move and rearrange quickly. When the film was cooled down, the alkyl group of higher α‐olefin units and LLDPE began to entangle and crystallize. Driven by crystallization, the PEG segments rearranged and enriched in the interface between the amphiphilic graft copolymer and air. By this surface modification method, the amphiphilic graft copolymer was fixed on the surface of LLDPE film. And the water contact angle was further reduced as low as 14.8°. The experimental results of this article demonstrate the potential pathway to provide an effective and durable anti‐fog LLDPE film. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface functionalization of polyolefin films via the ultraviolet‐induced photografting of acrylic acid: Topographical characterization and ability for binding antifungal agents

The photoinduced graft copolymerization of acrylic acid with ultraviolet radiation onto films of poly(vinyl chloride), polypropylene, and polyethylene was studied. Benzophenone was used as the initiator for most of the experiments performed. The percentage of grafting was determined by gravimetric measurements, and the characterization of the grafted films was carried out by chemical analysis (Fourier transform infrared spectroscopy, volumetric titration, and dye adsorption). In all samples, the grafted yield increased with the ultraviolet exposure time. High levels of grafting were obtained at room temperature. In addition, optical and atomic force microscopy allowed the topography of the modified films to be studied as a function of the reaction time. The pendant functional groups that were grafted were then used to bind antifungal agents, such as natamycin and crystal violet, and the antifungal properties of the films were demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:2254–2263, 2006     

Surface textures induced by convection in thin films of polymeric and polymerizable fluids

Thin liquid layers of polymer solutions, oligomers and monomers, and oligomer–monomer bilayers were used as model systems to explore the mechanism of formation of surface textures in solid coatings and films. It was shown that under particular conditions vertical temperature gradients imposed on these fluid layers induce in them various types of convection. We demonstrated that hexagonal patterns with a high degree of order and symmetry are generated in fluid films undergoing surface tension-driven convection. Various non-equilibrium textures have been trapped in the solid state either by vitrification induced by solvent evaporation from the fluid layer, or by carefully performed polymerization of monomers and oligomers. Finally, we demonstrated that convection patterns can be replicated in convection-passive fluids by bringing them in contact with a fluid layer undergoing convection.