Revisiting the Contribution of Additives to the Long-Term Mechanical Stability and Hydrolytic Resistance of Highly Crystalline Polylactide Fibers.

Additives are widely used to improve the processability, toughness, and hydrolytic resistance of poly(lactic acid) (PLA)-based materials. This study compares neat PLA fibers and fibers made from PLA blends with either poly(butylene succinate) (PBS) as a plasticizer or poly(d-lactic acid) (PDLA) as a nucleating agent. The fibers have been characterized with regard to their physical and structural properties after fabrication as well as after artificial aging at elevated temperature and humidity conditions. All samples have been fabricated using industrial melt-spinning equipment, resulting in a high crystallinity of about XC = 80% and a good initial toughness. Long-term relaxation behavior has been assessed with a self-developed lifetime prediction model, which is successfully verified for semicrystalline blended fibers. Despite slight improvement of the fiber elasticity and ductility, both types of blended fibers demonstrated a reduced hydrolytic resistance. These results suggest a design strategy for neat durable PLA fibers through processing-induced high crystallinity and orientation, which provide improved hydrolytic stability while preserving tough mechanical performance.

Volatile Aroma Surfactants: The Evaluation of the Adsorption-Evaporation Behavior under Dynamic and Equilibrium Conditions.

Multicomponent heterogeneous systems containing volatile amphiphiles are relevant to the fields ranging from drug delivery to atmospheric science. Research presented here discloses the individual interfacial activity and adsorption-evaporation behavior of amphiphilic aroma molecules at the liquid-vapor interface. The surface tension of solutions of nonmicellar volatile surfactants linalool and benzyl acetate, fragrances as such, was compared with that of the conventional surfactant sodium dodecyl sulfate (SDS) under equilibrium as well as under no instantaneous equilibrium, including a fast-adsorbing regime. In open systems, the increase in the surface tension on a time scale of ∼10 min is evaluated using a phenomenological model. The derived characteristic mass transfer constant is shown to be specific to both the desorption mechanism and the chemistry of the volatile amphiphile. Fast-adsorbing behavior disclosed here, as well as the synergetic effect in the mixtures with conventional micellar surfactants, justifies the advantages of volatile amphiphiles as cosurfactants in dynamic interfacial processes. The demonstrated approach to derive specific material parameters of fragrance molecules can be used for an application-targeted selection of volatile cosurfactants, e.g., in emulsification and foaming, inkjet printing, microfluidics, spraying, and coating technologies.

Tensiometry as a Simple Analytical Method for Quantification of Solubility and Release of Aroma Molecules in Aqueous Media.

Dynamic tensiometry is shown to be a high-potential analytical tool in assessing physico-chemical characteristics of fragrance molecules, such as solubility limit, volatility as well as much rarely assessed interfacial activity of these amphiphilic molecules. Surface tension of aqueous solutions of selected essential oils has been measured as a function of time and fragrance concentration using maximum bubble pressure method. The effect of the temperature and saline solution on the rate of dissolution in water was assessed. Dynamic surface tension turned to be sensitive to the composition of fragrances, as demonstrated on examples of natural and synthetic mixtures. Furthermore, presented work reveals the possibility of maximum bubble pressure tensiometry method to quantify the amount of fragrance compositions in flavored salts, including the artificially aged carrier samples. Suggested here analytical approach can be used for the detection of the purity of essential oils, for the optimization of compositions and of the manufacturing processes of fragrances-containing products, as well as for the assessment of the release/evaporation of fragrances from carrier systems.

Aroma Molecules as Dynamic Volatile Surfactants: Functionality beyond the Scent.

Understanding of nonequilibrium processes at dynamic interfaces is indispensable for advancing design and fabrication of solid-state and soft materials. The research presented here unveils specific interfacial behavior of aroma molecules and justifies their usage as multifunctional volatile surfactants. As nonconventional volatile amphiphiles, we study commercially available poorly water-soluble compounds from the classes of synthetic and essential flavor oils. Their disclosed distinctive feature is a high dynamic interfacial activity, so that they decrease the surface tension of aqueous solutions on a time scale of milliseconds. Another potentially useful property of such amphiphiles is their volatility, so that they notably evaporate from interfaces on a time scale of seconds. This behavior allows for control of wetting and spreading processes. A revealed synergetic interfacial behavior of mixtures of conventional and volatile surfactants is attributed to a decrease of the activation barrier as a result of high statistical availability of new sites at the surface upon evaporation of the volatile component. Our results offer promising advantages in manufacturing technologies which involve newly creating interfaces, such as spraying, coating technologies, ink-jet printing, microfluidics, laundry, and stabilization of emulsions in cosmetic and food industry, as well as in geosciences for controlling aerosol formation.

Synergic Swelling of Interactive Network Support and Block Copolymer Films during Solvent Vapor Annealing.

We report the effect of "interactive" polymer network (PN) supports on the solvent-vapor processing of thin polymer films. Densely cross-linked surface-attached network exhibits under experimental time scale a glassy swelling behavior with the conformational states and solvent-uptake clearly sensitive to the degree of solvent vapor saturation in the atmosphere. Pretreatment of the thermally cured PN films by complete immersion or by swelling in saturated chloroform vapors facilitates relaxation of the residual stresses and induces irreversible changes to the network structure as revealed by the swelling/deswelling tests. The presence of a polymer film on top of the PN support results in a mutual influence of the layers on the respective swelling kinetics, steady-state solvent uptake, and chain dynamics. Using UV-vis ellipsometry, we revealed a significantly faster swelling and higher solvent uptake of glassy PN layer below a polymer film as compared to a single PN layer on silicon substrate. Remarkably, the swelling of the network support continues to increase even when the overall swelling of the bilayer is in a steady-state regime. Block copolymer films on PN supports exhibit a faster ordering dynamics and exceptional stability toward dewetting as compared to similar films on silicon wafers. The mechanical stress produced by continuously swelling PN is suggested to account for the enhanced segmental dynamics even at low solvent concentration in the block copolymer film. Apart from novel insights into dynamics of solvent uptake by heterogeneous polymer films, these results might be useful in developing novel approaches toward fast-processing/annealing of functional polymer films and fibers.

Enzyme-Compatible Dynamic Nanoreactors from Electrostatically Bridged Like-Charged Surfactants and Polyelectrolytes.

Reported is an unanticipated mechanism of attractive electrostatic interactions of fully neutralized polyacrylic acid (PAA) with like-charged surfactants. Amphiphilic polymer-surfactant complexes with high interfacial activity and a solubilization capacity exceeding that of conventional micelles are formed by bridging with Ca2+ ions. Incorporation of a protease into such dynamic nanoreactors results in a synergistically enhanced cleaning performance because of the improved solubilization of poorly water-soluble immobilized proteins. Competitive interfacial and intermolecular interactions on different time- and length-scales have been resolved using colorimetric analysis, dynamic tensiometry, light scattering, and molecular dynamic simulations. The discovered bridging association mechanism suggests reengineering of surfactant/polymer/enzyme formulations of modern detergents and opens new opportunities in advancing labile delivery systems.

Morphology-Controlled Kinetics of Solvent Uptake by Block Copolymer Films in Nonselective Solvent Vapors.

We compare the swelling behavior of a compositionally symmetric diblock copolymer in films with nonbulk micellar morphology and with vertically oriented lamellae. The morphologies preformed by spin-coating from selective/nonselective solvents differ in shape and total area of the AB interfaces between incompatible units. Experimental measurements and dissipative particle dynamics (DPD) simulations demonstrate that AB interfaces dominate as the diffusion pathways of nonselective solvent molecules in strongly segregated films. In experiments, the lamellar films swell about 20× faster as compared to densely packed micellar structures, while the degrees of swelling at saturation are equal for the two types of morphologies. The difference in the kinetics of solvent uptake vanishes as soon as the solvent plasticizing effect allows for micelles-to-lamellae transition. DPD simulations confirm the inhomogeneous distribution of the solvent inside the film, with the higher fraction of the solvent localized at the AB interface and reveal morphology-dependent kinetics of the solvent uptake. The effect of dissimilar abilities of the nanodomains and of AB interface to serve as diffusion pathways for small molecules may find potential in designing nanosensors and heterogeneous barrier layers.