A Scalable and Surfactant-Free Emulsion Method for Producing Microbeads from Varied Biomass Feedstocks.

Despite national and international regulations, plastic microbeads are still widely used in personal care and consumer products (PCCPs). These exfoliants and rheological modifiers cause significant microplastic pollution in natural aquatic environments. Microbeads from nonderivatized biomass like cellulose and lignin can offer a sustainable alternative to these nondegradable microplastics, but processing this biomass into microbeads is challenging due to limited viable solvents and high biomass solution viscosities. To produce biomass microbeads of the appropriate size range for PCCPs (ca. 200-800 µm diameter) with shapes and mechanical properties comparable to those of commercial plastic microbeads, we used a surfactant-free emulsion/precipitation method, mixing biomass solutions in 1-ethyl-3-methylimidazolium acetate (EMImAc) with various oils and precipitating with ethanol. While yield of microbeads within the target size range highly depends on purification conditions, optimized protocols led to >90% yield of cellulose microbeads. Kraft lignin was then successfully incorporated into beads at up to 20 wt %; however, higher lignin contents result in emulsion destabilization unless surfactant is added. Finally, the microbead shape and surface morphology can be tuned using oils of varying viscosities and interfacial tensions. Dripping measurements and pendant drop tensiometry confirmed that the higher affinity of cellulose for certain oil/IL interfaces largely controlled the observed surface morphology. This work thus outlines how biomass composition, oil viscosity, and interfacial properties can be altered to produce more sustainable microbeads for use in PCCPs, which have desirable mechanical properties and can be produced over a wide range of shapes and surface morphologies.

Criteria Governing Rod Formation and Growth in Nonionic Polymer Micelles.

Self-assembled wormlike micelles (WLMs) are widely studied in small-molecule surfactants due to their unique ability to break and recombine; however, less is known about the structure and dynamics of nonionic polymer WLMs. Here, solutions of seven triblock poloxamers, composed of poly(propylene oxide) (PPO) midblocks and poly(ethylene oxide) (PEO) end blocks, are comprehensively examined to determine the role of poloxamer composition, temperature, and inorganic salt type and concentration on rod formation and subsequent elongation into WLMs. Phase separation and sphere-to-rod transition temperatures were quantified via cloud point measurements and shear rheology, respectively, and corroborated with small-angle neutron scattering (SANS). The local microstructure of resulting rodlike micelles is remarkably similar across poloxamer type and sodium fluoride (NaF) or sodium chloride (NaCl) content. Salt addition reduces transition temperatures, with the most pronounced effects for poloxamers with high PEO molecular weights and PEO fractions. Between these two temperatures, several poloxamers elongate into WLMs, where shear rheology detects increases in viscosity up to 6 orders of magnitude. Despite similar local microstructures, poloxamer identity and salt content impact micelle growth substantially, where large poloxamers with lower PEO fractions exhibit the highest viscosities and longest relaxation times. While sodium fluoride has little impact on micelle growth, increasing NaCl concentration dramatically increases the WLM viscosity and relaxation time. This result is explained by different interactions of each salt with the micelle: whereas NaF interacts primarily with PEO chains, NaCl may also partition to the PPO/PEO interface in low levels, increasing micelle surface tension, scission energy, and contour length.

Evaporation-controlled dripping-onto-substrate (DoS) extensional rheology of viscoelastic polymer solutions.

Extensional flow properties of polymer solutions in volatile solvents govern many industrially-relevant coating processes, but existing instrumentation lacks the environment necessary to control evaporation. To mitigate evaporation during dripping-onto-substrate (DoS) extensional rheology measurements, we developed a chamber to enclose the sample in an environment saturated with solvent vapor. We validated the evaporation-controlled DoS device by measuring a model high molecular weight polyethylene oxide (PEO) in various organic solvents both inside and outside of the chamber. Evaporation substantially increased the extensional relaxation time [Formula: see text] for PEO in volatile solvents like dichloromethane and chloroform. PEO/chloroform solutions displayed an over 20-fold increase in [Formula: see text] due to the formation of an evaporation-induced surface film; evaporation studies confirmed surface features and skin formation reminiscent of buckling instabilities commonly observed in drying polymer solutions. Finally, the relaxation times of semi-dilute PEO/chloroform solutions were measured with environmental control, where [Formula: see text] scaled with concentration by the exponent [Formula: see text]. These measurements validate the evaporation-controlled DoS environment, and confirm that chloroform is a good solvent for PEO, with a Flory exponent of [Formula: see text]. Our results are the first to control evaporation during DoS extensional rheology, and provide guidelines establishing when environmental control is necessary to obtain accurate rheological parameters.