Mechanochromic and Thermochromic Sensors Based on Graphene Infused Polymer Opals.

High quality opal-like photonic crystals containing graphene are fabricated using evaporation-driven self-assembly of soft polymer colloids. A miniscule amount of pristine graphene within a colloidal crystal lattice results in the formation of colloidal crystals with a strong angle-dependent structural color and a stop band that can be reversibly shifted across the visible spectrum. The crystals can be mechanically deformed or can reversibly change color as a function of their temperature, hence their sensitive mechanochromic and thermochromic response make them attractive candidates for a wide range of visual sensing applications. In particular, it is shown that the crystals are excellent candidates for visual strain sensors or integrated time-temperature indicators which act over large temperature windows. Given the versatility of these crystals, this method represents a simple, inexpensive, and scalable approach to produce multifunctional graphene infused synthetic opals and opens up exciting applications for novel solution-processable nanomaterial based photonics.

Surface characterization of drying acrylic latex dispersions with variable methacrylic acid content using surface dilatational rheology.

HYPOTHESIS: Drying of latex dispersions often results in particle gradients at the latex-air interface. We expect that, by increasing the carboxylic acid content of latex particles, inter-particle interactions at the interface change. With dilatational rheology one could detect particle-particle interactions in an early stage of the drying process and elucidate the nature of these interactions. EXPERIMENTS: Acrylic latex dispersions were prepared with different amounts of methacrylic acid (MAA), ranging from 2 to 10 wt% on dry mass. Dilatational rheology studies during drying at different relative humidities RH were performed using profile analysis tensiometry. Visco-elastic properties of latex surfaces were used to identify inter-particle interactions at the surfaces depending on the drying rate and particle composition. FINDINGS: Drying at 85% RH did not show significant changes of the mechanical properties of the latex surfaces. Drying at 65 and 53% RH resulted in a change of the mechanical properties, ultimately showing non-linear visco-elastic behavior. This indicates that capillary and/or Van der Waals forces were operating between particles at the surface. With increasing MAA content the viscous contribution decreased, possibly due to the formation of more gel-like structures at the particle surface due to higher solubility of polymer segments near to the surface.

Film Formation of High Tg Latex Using Hydroplasticization: Explanations from NMR Relaxometry.

The film formation of acrylic latex dispersions, containing different amounts of carboxylic acid functional groups by the incorporation of methacrylic acid (MAA), was studied with GARField 1H NMR at various relative humidities (RH). Polymer particles with glass-transition temperatures in the range from 26 to 50 °C formed films at room temperature because of hydroplasticization. It was found that with an increased drying rate due to lower RH, the evaporation flux of water was limited by the latex polymer. Only in the second stage of drying this phenomenon was more obvious with increasing MAA content. 1H NMR relaxometry was used to study the change of hydrogen mobilities during film formation and hardening of the films. This showed that the drying rate itself had no impact on the hydrogen mobility in the latex films as measured via the T2 relaxation time. Hydrogen mobilities of water and the mobile polymer phase only significantly decrease after most water has evaporated. This implies that the rigidity of the polymers increases with the evaporation of water that otherwise plasticizes the polymer through hydrogen bonding with the carboxylic acid groups. This hardening of the polymer phase is essential for applications in a coating. The hydrogen mobilities were affected by the MAA concentration. Densities of mobile hydrogens increase with increasing MAA content. This is expected if the mobile protons are contained in the MAA groups. The result thus confirms the role of carboxylic acid groups in hydrogen bonding and plasticization of the copolymers. Hydrogen mobilities, however, decrease with increasing MAA content, which is hypothesized to be caused by the formation of dimers of carboxylic acid groups that still hold water. They still enable short-range polymer hydrogen mobility due to hydroplasticization but limit long-range polymer mobility due to interaction between the carboxylic acid groups.

Water Vapor Sorption and Diffusion in Secondary Dispersion Barrier Coatings: A Critical Comparison with Emulsion Polymers.

The conventional method for synthesizing waterborne polymer colloids is emulsion polymerization using surfactants. An emerging method is the use of secondary dispersions (SD) of polymers in water, which avoids the addition of any surfactant. Although there are numerous studies of the water barrier properties (sorption, diffusion, and permeability) of waterborne emulsion (Em) polymer coatings, the properties of SD coatings, in comparison, have not been thoroughly investigated. Here, dynamic water vapor sorption analysis is used to compare the equilibrium sorption isotherms of the two forms of styrene-acrylate copolymers (Em and SD) with the same monomer composition. From an analysis of the kinetics of vapor sorption, the diffusion coefficient of water in the polymer coatings is determined. The combined effects of particle boundaries and surfactant addition were investigated through a comparison of the properties of SD and Em coatings to those of (1) solvent-cast polymer coatings (of the same monomer composition), (2) Em polymers that underwent dialysis to partially remove the water-soluble species, and (3) SD polymers with added surfactants. The results reveal that both the particle boundaries and the surfactants increase vapor sorption. The diffusion coefficients of water are comparable in magnitude in all of the polymer systems but are inversely related to water activity because of molecular clustering. Compared to all of the other waterborne polymer systems, the SD barrier coatings show the lowest equilibrium vapor sorption and permeability coefficients at high relative humidities as well as the lowest water diffusion coefficient at low humidities. These barrier properties make SD coatings an attractive alternative to conventional emulsion polymer coatings.