A Study of Headspace Solid-Phase Microextraction in the Analysis of 54 Hydrophobic Pollutants in Remote Alpine Lake Waters with an Emphasis on Analyte Recovery and Storage Time.

Commercially available headspace solid-phase microextraction (HS-SPME) fibers have been used for years to extract pesticides and polychlorinated biphenyls from aqueous samples at the expected ultratrace levels (picograms per liter or parts per quadrillion) in alpine lakes. Several variables of the HS-SPME technique have been adequately evaluated, including water temperature, pH, salt content, fiber type and coating thickness, length of fiber-sample exposure, and liquid immersion versus headspace exposure; but surprisingly, analyte recovery as a function of analyte concentration and storage time has not been included in previous studies, which can be important for remote sampling sites. Seven hydrophobic chlorinated pollutants were identified in alpine lake water (out of 54 analyzed); but recovery using the common SPME technique was found to be inconsistent as the analyte concentration decreases, and the recovery trend as a function of concentration varies on a compound-to-compound basis that could result in a large underestimation of analyte concentrations in field samples. Of the 54 compounds surveyed, o,p'-dichlorodiphenyltrichloroethane (DDT), p,p'-DDT, p,p'-dichlorodiphenyldichloroethylene (DDE), o,p'-DDE, chlorthal-dimethyl, endosulfan I, γ-hexachlorocyclohexane, heptachlor, and trans-nonachlor were generally measured at concentrations between 1 and 150 pg/L (parts per quadrillion). No study to date has evaluated this commonly used but unstandardized technique for analyte recovery as a function of analyte concentration or storage time of aqueous samples. Environ Toxicol Chem 2023;42:1199-1211. © 2023 SETAC.

Colloidal Gelation in Liquid Metals Enables Functional Nanocomposites of 2D Metal Carbides (MXenes) and Lightweight Metals.

Nanomaterials dispersed in different media, such as liquids or polymers, generate a variety of functional composites with synergistic properties. In this work, we discuss liquid metals as the nanomaterials' dispersion media. For example, 2D transition-metal carbides and nitrides (MXenes) can be efficiently dispersed in liquid Ga and lightweight alloys of Al, Mg, and Li. We show that the Lifshitz theory predicts strong van der Waals attraction between nanoscale objects interacting through liquid metals. However, a uniform distribution of MXenes in liquid metals can be achieved through colloidal gelation, where particles form self-supporting networks stable against macroscopic phase segregation. This network acts as a reinforcement boosting mechanical properties of the resulting metal-matrix composite. By choosing Mg-Li alloy as an example of ultralightweight metal matrix and Ti3C2Tx MXene as a nanoscale reinforcement, we apply a liquid metal gelation technique to fabricate functional nanocomposites with an up to 57% increase in the specific yield strength without compromising the matrix alloy's plasticity. MXenes largely retain their phase and 2D morphology after processing in liquid Mg-Li alloy at 700 °C. The 2D morphology enables formation of a strong semicoherent interface between MXene and metal matrix, manifested by biaxial strain of the MXene lattice inside the metal matrix. This work expands applications for MXenes and shows the potential for developing MXene-reinforced metal matrix composites for structural alloys and other emerging applications with metal-MXene interfaces, such as batteries and supercapacitors.

Controlling shear jamming in dense suspensions via the particle aspect ratio.

Dense suspensions of particles in a liquid exhibit rich, non-Newtonian behaviors such as shear thickening (ST) and shear jamming (SJ). ST has been widely studied and is known to be enhanced by increasing the particles' frictional interactions and also by making their shape more anisotropic. SJ however has only recently been understood to be a distinct phenomenon and, while the role of interparticle friction has been investigated, the role of particle anisotropy in controlling the SJ regime has remained unknown. To address this we here synthesize silica particles for use in water/glycerol suspensions. This pairing of hydrogen-bonding particle surfaces and suspension solvent has been shown to elicit SJ with spherical particles. We then vary particle aspect ratio from Γ = 1 (spheres) to Γ = 11 (slender rods), and perform rheological measurements to determine the effect of particle anisotropy on the onset of shear jamming. We also show that the effect on the precursor to SJ, discontinuous shear thickening (DST), is consistent with prior work. We find that increasing aspect ratio significantly reduces φm, the minimum particle packing fraction at which SJ can be observed, to values as low φm = 33% for Γ = 11. The ability to fix the properties of the solvated particle surfaces, and thus the particle interactions at contact, while varying shape anisotropy, yields fundamental insights about the SJ capabilities of suspensions and provides a framework to rationally design and tune these behaviors.

Tuning Interparticle Hydrogen Bonding in Shear-Jamming Suspensions: Kinetic Effects and Consequences for Tribology and Rheology.

The reversible shear-induced solidification of dense suspensions, known as shear jamming, critically depends on frictional interparticle contacts. Recently, it was shown that shear jamming can be strongly affected by molecular-scale interactions between particles, e.g., by chemically controlling their propensity for hydrogen bonding. However, hydrogen bonding not only enhances interparticle friction but also introduces (reversible) adhesion, whose interplay with friction in shear-jamming systems has so far remained unclear. Here, we present atomic force microscopy studies to assess interparticle adhesion, its relationship to friction, and how these attributes are influenced by urea, a molecule that interferes with hydrogen bonding. We characterize the kinetics of this process with nuclear magnetic resonance, relating it to the time dependence of the macroscopic flow behavior with rheological measurements. We find that time-dependent urea sorption reduces friction and adhesion, causing a reduction in the high-shear viscosity. These results extend our mechanistic understanding of chemical effects on the nature of shear jamming, promising new avenues for fundamental studies and applications alike.

Stress Controlled Rheology of Dense Suspensions Using Transient Flows.

Dense suspensions of hard particles in a Newtonian liquid can be jammed by shear when the applied stress exceeds a certain threshold. However, this jamming transition from a fluid into a solidified state cannot be probed with conventional steady-state rheology because the stress distribution inside the material cannot be controlled with sufficient precision. Here we introduce and validate a method that overcomes this obstacle. Rapidly propagating shear fronts are generated and used to establish well-controlled local stress conditions that sweep across the material. Exploiting such transient flows, we can track how a dense suspension approaches its shear-jammed state dynamically and quantitatively map out the onset stress for solidification in a state diagram.

Interparticle hydrogen bonding can elicit shear jamming in dense suspensions.

Dense suspensions of hard particles in a liquid can exhibit strikingly counter-intuitive behaviour, such as discontinuous shear thickening (DST)1-7 and reversible shear jamming (SJ) into a state where flow is arrested and the suspension is solid-like8-12. A stress-activated crossover from hydrodynamic interactions to frictional particle contacts is key for these behaviours2-4,6,7,9,13. However, in experiments, many suspensions show only DST, not SJ. Here we show that particle surface chemistry plays a central role in creating conditions that make SJ readily observable. We find the system's ability to form interparticle hydrogen bonds when sheared into contact elicits SJ. We demonstrate this with charge-stabilized polymer microspheres and non-spherical cornstarch particles, controlling hydrogen bond formation with solvents. The propensity for SJ is quantified by tensile tests12 and linked to an enhanced friction by atomic force microscopy. Our results extend the fundamental understanding of the SJ mechanism and open avenues for designing strongly non-Newtonian fluids.