Tunable distribution of silica nanoparticles in water-borne coatings via strawberry supracolloidal dispersions.

HYPOTHESIS: Water-borne coatings are rapidly expanding as sustainable alternatives to organic solvent-borne systems. Inorganic colloids are often added to aqueous polymer dispersions to enhance the performance of water-borne coatings. However, these bimodal dispersions have many interfaces which can result in unstable colloids and undesirable phase separation. The covalent bonding between individual colloids, on a polymer-inorganic core-corona supracolloidal assembly, could reduce or suppress instability and phase separation during drying of coatings, advancing its mechanical and optical properties. METHODS: Aqueous polymer-silica supracolloids with a core-corona strawberry configuration were used to precisely control the silica nanoparticles distribution within the coating. The interaction between polymer and silica particles was fine-tuned to obtain covalently bound or physically adsorbed supracolloids. Coatings were prepared by drying the supracolloidal dispersions at room temperature, and their morphology and mechanical properties were interconnected. FINDINGS: Covalently bound supracolloids provided transparent coatings with a homogeneous 3D percolating silica nanonetwork. Supracolloids having physical adsorption only, resulted in coatings with a stratified silica layer at interfaces. The well-arranged silica nanonetworks strongly improve the storage moduli and water resistance of the coatings. These supracolloidal dispersions offer a new paradigm for preparing water-borne coatings with enhanced mechanical properties and other functionalities, like structural color.

Assembly of partially covered strawberry supracolloids in dilute and concentrate aqueous dispersions.

HYPOTHESIS: Core-corona supracolloids can be assembled in aqueous dispersions by controlling the physical interactions between the corona and core colloidal particles. A raspberry corona configuration with full surface coverage of the core can be reached by inducing strong attractive interactions between the individual particles. A controlled partial surface coverage of the core, i.e. strawberry configuration, is however, more difficult to achieve. Supracolloids with different surface coverage ratio exhibit unique and multifunctional surface properties. EXPERIMENTS: By counterbalancing the multiple physical interactions playing a role during the assembly, the configuration and stability of the assemblies could be fine-tuned over a wide range of concentrations. Supracolloids consisting of polyethylene glycol (PEO)-grafted polymer particles covered by silica nanoparticles were assembled with different configurations, by adjusting the pH and ionic strength of the dispersion, the PEO grafting density and the particles concentration. The self-assembly process and resulting configurations were monitored via cryogenic transmission electron microscopy (Cryo-TEM) and light scattering. FINDINGS: The suitable conditions to assemble supracolloids with partial corona coverage have been established. Stable strawberry supracolloids could be prepared, both for diluted (1 wt%) and concentrated (12 wt%) dispersions. These hybrid supracolloids with well-defined configuration are highly relevant to developing advanced water-borne paints and inks, food dispersions, cosmetic and healthcare products.

Distribution of block copolymers in drying polymer films.

HYPOTHESIS: Block copolymers (BCP) consisting of a polar block and a surface active apolar block are widely used for surface functionalization of polymer films. The characteristics of the copolymer blocks determine whether surface segregation and/or phase separation occurs, for a given bulk mixture. This data can be used to find the optimal BCP composition where high surface enrichment is obtained without accumulation of phase separated BCP in the bulk. METHODS: The distribution of poly(ethylene oxide)-polydimethylsiloxane (PEO-PDMS) BCP in a polymer formulation relevant for coating applications is systematically investigated. The surface segregation is studied in liquid formulations with surface tension measurements and dried films with X-ray photoelectron spectroscopy (XPS), whereas phase separation is quantified using turbidity measurements. The results are compared with Scheutjens-Fleer self-consistent field (SF-SCF) computations, which are also applied to determine the effect of film drying on BCP phase stability and surface segregation. FINDINGS: Longer PDMS blocks result in lower interfacial tension of the liquid polymer mixture, whereas for the cured films, the largest PDMS concentration at the interface was obtained for intermediate PDMS block lengths. This is explained by the observation that phase separation already occurs at very low BCP concentrations for long PDMS blocks. The SCF predictions qualitatively agree with the experimental results and reveal that the BCP distribution changes significantly during film drying.

Water Swelling Behavior of Poly(ethylene glycol)-Based Polyurethane Networks.

Defects in a polymer network complicate an accurate calculation of structural parameters such as the molar mass between cross-links M c, typically obtained from experimental swelling data. In this paper the formation and structure of poly(ethylene glycol) (PEG)-based polyurethane networks containing PEG-mono methyl ether dangling chains are studied. The phantom network model can describe the swelling behavior of these networks only when a composition-dependent interaction parameter is used and the formation of allophanates is accounted for. A clear transition in the network formation is found at the PEG network precursor molar mass at which entanglements are formed in the melt. Correction factors based on structure calculations using the Miller-Macosko-Vallés probability approach are proposed and validated for an accurate calculation of the M c of these defect-containing networks. This provides a new approach for studies that requires an accurate estimate of the M c, only based on experimentally straightforward swelling experiments.

Quantitative Conductive Atomic Force Microscopy on Single-Walled Carbon Nanotube-Based Polymer Composites.

Conductive atomic force microscopy (C-AFM) is a valuable technique for correlating the electrical properties of a material with its topographic features and for identifying and characterizing conductive pathways in polymer composites. However, aspects such as compatibility between tip material and sample, contact force and area between the tip and the sample, tip degradation and environmental conditions render quantifying the results quite challenging. This study aims at finding the suitable conditions for C-AFM to generate reliable, reproducible, and quantitative current maps that can be used to calculate the resistance in each point of a single-walled carbon nanotube (SWCNT) network, nonimpregnated as well as impregnated with a polymer. The results obtained emphasize the technique's limitation at the macroscale as the resistance of these highly conductive samples cannot be distinguished from the tip-sample contact resistance. Quantitative C-AFM measurements on thin composite sections of 150-350 nm enable the separation of sample and tip-sample contact resistance, but also indicate that these sections are not representative for the overall SWCNT network. Nevertheless, the technique was successfully used to characterize the local electrical properties of the composite material, such as sample homogeneity and resistance range of individual SWCNT clusters, at the nano- and microscale.

Kinetic Monte Carlo simulation of the photodegradation process of polyester-urethane coatings.

A numerical method to simulate reactions in a cross-linked polymer is developed and applied to the photodegradation process of polyester-urethane clearcoats during artificial exposure in a Weather-Ometer. This coarse-grained simulation method, which is based on a kinetic Monte Carlo scheme, is verified with experimental data on the depth-resolved changes in optical properties and chemical composition that have been previously determined. By modelling the depth-dependency of physical processes that occur in the coating, such as the absorption of photons and the diffusion of oxygen, the experimentally observed evolution of depth gradients in chemical composition can be well described by the simulation. A sensitivity analysis of individual simulation input parameters with respect to a set of resulting observables is performed and the results provide insight into the influence of specific reaction mechanisms on the overall degradation process and help to distinguish essential from less important processes. The values of input parameters that result in the most accurate simulation of the experimental data are determined with an optimisation procedure. In this way, the numerical values of several kinetic and physical parameters that are difficult to determine directly in an experimental way, such as various reaction rate constants, can be obtained from the simulations.

The corrosion protection of AA2024-T3 aluminium alloy by leaching of lithium-containing salts from organic coatings.

Lithium carbonate and lithium oxalate were incorporated as leachable corrosion inhibitors in model organic coatings for the protection of AA2024-T3. The coated samples were artificially damaged with a scribe. It was found that the lithium-salts are able to leach from the organic coating and form a protective layer in the scribe on AA2024-T3 under neutral salt spray conditions. The present paper shows the first observation and analysis of these corrosion protective layers, generated from lithium-salt loaded organic coatings. The scribed areas were examined by scanning and transmission electron microscopy before and after neutral salt spray exposure (ASTM-B117). The protective layers typically consist of three different layered regions, including a relatively dense layer near the alloy substrate, a porous middle layer and a flake-shaped outer layer, with lithium uniformly distributed throughout all three layers. Scanning electron microscopy and white light interferometry surface roughness measurements demonstrate that the formation of the layer occurs rapidly and, therefore provides an effective inhibition mechanism. Based on the observation of this work, a mechanism is proposed for the formation of these protective layers.

Hierarchical multi-scale simulations of adhesion at polymer-metal interfaces: dry and wet conditions.

We performed hierarchical multi-scale simulations to study the adhesion properties of various epoxy-aluminium interfaces in the absence and presence of water. The epoxies studied differ from each other in their hexagonal ring structures where one contains aromatic and the other aliphatic rings. As aluminium is unavoidably covered with alumina, a cross-linked epoxy structure near an alumina substrate is created and relaxed by performing coarse-grained simulations. To that purpose, we employ a recently developed parameterization method for variable bead sizes. For polymer-metal interactions, a multi-scale parameterization scheme is applied where the relative adsorption of each bead type is quantified. At the mesoscopic scale, the adhesion properties of different epoxy systems are discussed in terms of their interfacial structure and adsorption behavior. To further perform all-atom simulations, the mesoscopic structures are transformed into atomistic coordinates by applying a reverse-mapping procedure. Interface internal energies are quantified and the simulation results observed at different scales are compared with each other as well as with the available experimental data. The good agreement between observations from simulations and experiments shows the usefulness of such an approach to better understand polymer-metal oxide adhesion.

Significance of the amide functionality on DOPA-based monolayers on gold.

The adhesive proteins secreted by marine mussels contain an unusual amino acid, 3,4-dihydroxyphenylalanine (DOPA), that is responsible for the cohesive and adhesive strength of this natural glue and gives mussels the ability to attach themselves to rocks, metals, and plastics. Here we report a detailed structural and spectroscopic investigation of the interface between N-stearoyldopamine and a single-crystalline Au(111) model surface and an amide-absent molecule, 4-stearylcatechol, also on Au(111), with the aim of understanding the role of the amide functionality in the packing, orientation, and fundamental interaction between the substrate and the monolayer formed from an aqueous environment by the Langmuir-Blodgett technique. The organization of monolayers on gold was observed directly and studied in detail by X-ray photoelectron spectroscopy (XPS), contact angle measurements (CA), surface-enhanced Raman spectroscopy (SERS), infrared reflection-absorption spectroscopy (IRRAS), and atomic force microscopy (AFM). Our study shows that within the monolayer the catecholic oxygen atoms are coordinated to the gold surface, having a more perpendicular orientation with respect to the aromatic ring and the apparently tilted alkyl chains, whereas the amide functionality stabilizes the monolayer that is formed.

Depth characterization of photopolymerized films by confocal Raman microscopy using an immersion objective.

The depth characterization of photopolymer films by confocal Raman microscopy is often troublesome due to refraction effects. To minimize these effects, we used an oil immersion objective and a method was developed to avoid penetration of the oil without damaging the sample surface. Since the surface may be sticky if oxygen in the air inhibits the photopolymerization, a protective layer could not be put onto the film. Therefore, the method consists in using a thin polypropylene foil as substrate for the coating and placing the sample upside down under the objective. In this manner, the immersion oil could be deposited on top of the polypropylene. The advantage of this setup is that the oil, polypropylene substrate, and photopolymer film have close refractive indices. Basic calculations showed that the depth resolution is hardly affected in that configuration and double-bond conversion profiles could be plotted as a function of reliable nominal depth. The validity of the methodology was confirmed by experiments carried out with a dry metallurgical objective on the sample surface, face up, where refraction effects are still minor. In addition, infrared spectroscopy, which was used to follow the photopolymerization, corroborated the Raman conversion of the films over their thickness. The confocal Raman microscopy method can be applied to various photopolymerized systems to characterize their behavior towards oxygen inhibition and other heterogeneities in conversion arising from inner filter effects or interactions between additives for instance.