3D printing of polyvinyl alcohol hydrogels enabled by aqueous two-phase system.

The synthesis of PVA hydrogels (PVA-Hy) requires a highly basic environment (e.g., an aqueous solution of sodium hydroxide, NaOH, 14% w/w, 4.2 M), but the rapid crosslinking of PVA due to high pH makes it challenging to perform layer-by-layer three-dimensional (3D) printing of PVA-Hy. This work demonstrated 3D printing of PVA-Hy in moderate alkaline conditions (e.g., NaOH, 1% w/w, 0.3 M) assisted by aqueous two-phase system (ATPS). Salting out of PVA to form ATPS allowed temporal shape retention of a 3D-printed PVA structure while it was physically crosslinked in moderate alkaline conditions. Crucially, the layer-to-layer adhesion of PVA was facilitated by delayed crosslinking of PVA that required additional reaction time and overlapping between the layers. To verify this principle, we studied the feasibility of direct ink write (DIW) 3D printing of PVA inks (5-25% w/w, µ = 0.1-20 Pa s, and MW = 22 000 and 74 800) in aqueous embedding media offering three distinct chemical environments: (1) salts for salting out (e.g., Na2SO4), (2) alkali hydroxides for physical crosslinking (e.g., NaOH), and (3) a mixture of salt and alkali hydroxide. Our study suggested the feasibility of 3D-printed PVA-Hy using the mixture of salt and alkali hydroxide, demonstrating a unique concept of embedded 3D printing enabled by ATPS for temporary stabilization of the printed structures to facilitate 3D fabrication.

2D/2D Heterojunction of BiOBr/BiOI Nanosheets for In Situ H2 O2 Production and Activation toward Efficient Photocatalytic Wastewater Treatment.

The presence of toxic organic pollutants in aquatic environments poses significant threats to human health and global ecosystems. Photocatalysis that enables in situ production and activation of H2 O2 presents a promising approach for pollutant removal; however, the processes of H2 O2 production and activation potentially compete for active sites and charge carriers on the photocatalyst surface, leading to limited catalytic performance. Herein, a hierarchical 2D/2D heterojunction nanosphere composed of ultrathin BiOBr and BiOI nanosheets (BiOBr/BiOI) is developed by a one-pot microwave-assisted synthesis to achieve in situ H2 O2 production and activation for efficient photocatalytic wastewater treatment. Various experimental and characterization results reveal that the BiOBr/BiOI heterojunction facilitates efficient electron transfer from BiOBr to BiOI, enabling the one-step two-electron O2 reduction for H2 O2 production. Moreover, the ultrathin BiOI provides abundant active sites for H2 O2 adsorption, promoting in situ H2 O2 activation for •O2 - generation. As a result, the BiOBr/BiOI hybrid exhibits excellent activity for pollutant degradation with an apparent rate constant of 0.141 min-1 , which is 3.8 and 47.3 times that of pristine BiOBr and BiOI, respectively. This work expands the range of the materials suitable for in situ H2 O2 production and activation, paving the way toward sustainable environmental remediation using solar energy.

Droplet detachment force and its relation to Young-Dupre adhesion.

Droplets adhere to surfaces due to their surface tension γ and understanding the vertical force Fd required to detach the droplet is key to many technologies (e.g., inkjet printing, optimal paint formulations). Here, we predicted Fd on different surfaces by numerically solving the Young-Laplace equation. Our numerical results are consistent with previously reported results for a wide range of experimental conditions: droplets subjected to surface vs. body forces with |Fd| ranging from nano- to milli-newtons, droplet radii R ranging from tens of microns to several millimetres, and for various surfaces (micro-/nano-structured superhydrophobic vs. lubricated surfaces). Finally, we derive an analytic solution for Fd on highly hydrophobic surfaces and further show that for receding contact angle θr > 140°, the normalized Fd/πR is equivalent to the Young-Dupre work of adhesion γ(1 + cos θr).

Energy Loss for Droplets Bouncing Off Superhydrophobic Surfaces.

A water droplet can bounce off superhydrophobic surfaces multiple times before coming to a stop. The energy loss for such droplet rebounds can be quantified by the ratio of the rebound speed UR and the initial impact speed UI; i.e., its restitution coefficient e = UR/UI. Despite much work in this area, a mechanistic explanation for the energy loss for rebounding droplets is still lacking. Here, we measured e for submillimeter- and millimeter-sized droplets impacting two different superhydrophobic surfaces over a wide range of UI (4-700 cm s-1). We proposed simple scaling laws to explain the observed nonmonotonic dependence of e on UI. In the limit of low UI, energy loss is dominated by contact-line pinning and e is sensitive to the surface wetting properties, in particular to contact angle hysteresis Δ cos θ of the surface. In contrast, e is dominated by inertial-capillary effects and does not depend on Δ cos θ in the limit of high UI.

Presence, origins and effect of stable surface hydration on regenerated cellulose for underwater oil-repellent membranes.

HYPOTHESIS: Underwater oil-repellency of polyelectrolyte brushes has been attributed mainly to electric double-layer repulsion forces based on Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Many non-polyelectrolyte materials also exhibit oil-repellent behaviour, but it is not clear if there exist similar electric double-layer repulsion and if it is the sole mechanism governing their underwater oil-repellency. EXPERIMENTS/SIMULATIONS: In this article, the oil-repellency of highly amorphous cellulose exhibiting is investigated in detail, through experiments and molecular dynamics simulations (MDS). FINDINGS: It was found that the stable surface hydration on regenerated cellulose was due to a combination of long-range electrostatic repulsions (DLVO theory) and short-range interfacial hydrogen bonding between cellulose and water molecules (as revealed by MDS). The presence of a stable water layer of about 200 nm thick (similar to that of polyelectrolyte brushes) was confirmed. Such stable surface hydration effectively separates cellulose surface from oil droplets, resulting in extremely low adhesion between them. As a demonstration of its practicality, regenerated cellulose membranes were fabricated via electrospinning, and they exhibit high oil/water separation efficiencies (including oil-in-water emulsions) as well as self-cleaning ability.

Quantifying Surface Wetting Properties Using Droplet Probe Atomic Force Microscopy.

The functional properties of a surface, such as its anti-fogging or anti-fouling performance, are influenced by its wettability. To quantify surface wettability, the most common approach is to measure the contact angles of a liquid droplet on the surface. While well established and relatively easy to perform, contact angle measurements were developed to describe macroscopic wetting properties and are difficult to perform for submillimetric droplets. Moreover, they cannot spatially resolve surface heterogeneities that can contribute to surface fouling. To address these shortcomings, we report on using an atomic force microscopy technique to quantitatively measure the interaction forces between a microdroplet and a surface with piconewton force resolution. We show how our technique can be used to spatially map topographical and chemical heterogeneities with micron resolution.