Hybrid films from plant and bacterial nanocellulose: mechanical and barrier properties

The accumulation of petroleum polymers compromises biodiversity and causes environmental problems. Nanocellulose enhances biodegradability and can improve the physical-mechanical performance of materials. The objective was to produce and characterize hybrid films composed of bacterial cellulose (BC) and plant nanocellulose from Eucalyptus (Euc) or Pinus (Pin). Films were produced by the casting method using filmogenic suspensions with different cellulose nanofibrils (CNFs) proportions from both the sources (0, 25, 50, 75 and 100 %). CNFs suspensions were characterized by transmission electron microscopy. The morphology of the films was analyzed using scanning electron microscopy. In addition, the transparency, contact angle, wettability, oil and water vapor barrier and mechanical properties were also evaluated. The contact angles were smaller for films with BC and the wettability was greater when comparing BC with plant CNFs (0.10 ° s − 1 {\text{s}^{-1}} for 75 % Euc/25 % BC and 0.20 ° s − 1 {\text{s}^{-1}} for 25 % Euc/75 % BC). The water vapor permeability (WVP) of the 100 % BC films and the 25 % Euc/75 % BC composition were the highest among the studied compositions. Tensile strength, Young’s modulus and puncture strength decreased considerably with the addition of BC in the films. More studies regarding pre-treatments to purify BC are needed to improve the mechanical properties of the films.

A Novel Biomimetic Nanocomposite Exhibiting Petal Wetting Phenomenon: Fabrication and Experimental Investigations

A functional composite material that simultaneously exhibits hydrophobicity and water droplet adhesion has monumental potential in controlling fluid flow, studying phase separation, and biological research. This article reports the fabrication of a petal wetting biomimetic Boron Nitride Nanotubes (BNNTs) -Polydimethylsiloxane (PDMS) nanocomposite achieved by drop casting. The petal effect was investigated by non-destructive techniques. The nanotubes were synthesized by chemical vapor deposition at 1150 °C and were characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The mean diameter of the nanotubes was found to be 70 nm. The nanocomposites had BNNT fillers ranging from 0.5 wt. % to 2 wt. %. Water contact angles for pure PDMS polymer was 94.7° and for the 2 wt. % BNNT-PDMS nanocomposite was 132.4°. The petal wetting nanocomposite displayed a characteristic trait of high contact angle hysteresis. The surface roughness parameters of the nanocomposites were determined by atomic force microscopy. Laser scanning confocal microscopy aided in analyzing the droplet penetration and in observing the trapped air between the water droplet and the nanocomposite surface. Based on surface observations, roughness parameters, and the extent of droplet penetration by the surface, we shed light on the Cassie impregnating wetting regime followed by the biomimetic nanocomposite. Such a surface would be beneficial in the study of the embryogenesis of cells and aid in moisture collection.

Water–propylene glycol sessile droplet shapes and migration: Marangoni mixing and separation of scales

New light is shed on morphological features of water–propylene glycol sessile droplets evaporating into ambient air at not too high relative humidity. Such droplets adopt a Marangoni-contracted shape even on perfectly wetting substrates, an effect well known since Cira et al. (Nature, 519, 2015). We here highlight a strong separation of scales normally occurring for such droplets. Namely, there is a narrow high-curvature zone localized at the foot of the droplet, where the apparent contact angle is formed, while the core of the droplet merely adheres to the classical (capillary–gravity) static shape. Experimentally, we rely upon interferometry to discern such fine key details. We detect a maximum of the droplet slope profile in the foot region, which amounts to the apparent contact angle. Theoretically, a local description of the foot region is devised. We indicate a crucial role of convective mixing by the solutal Marangoni flow, here accounted for by the Taylor dispersion, which proves to underlie the separation of scales and ensure self-consistency of the local model. Migration of such droplets in a humidity gradient is also approached within the same experimental and theoretical framework. It is considered that the resulting back–front asymmetry of the apparent contact angles drives the motion similarly to a wettability gradient, although the drag (‘Cox–Voinov’) factor is here found to be different. The predictions, comparing well with the measurements (our own and from the literature), are based on rigorous models, isothermal and as reduced as possible, without any fitting parameters or microphysics effects.

Three-Dimensional Soft Material Micropatterning via Grayscale Photolithography for Improved Hydrophobicity of Polydimethylsiloxane (PDMS)

In this present work, we aim to improve the hydrophobicity of a polydimethylsiloxane (PDMS) surface. Various heights of 3D PDMS micropillars were fabricated via grayscale photolithography, and improved wettability was investigated. Two approaches of PDMS replication were demonstrated, both using a single master mold to obtain the micropillar arrays. The different heights of fabricated PDMS micropillars were characterized by scanning electron microscopy (SEM) and a surface profiler. The surface hydrophobicity was characterized by measuring the water contact angles. The fabrication of PDMS micropillar arrays was shown to be effective in modifying the contact angles of pure water droplets with the highest 157.3-degree water contact angle achieved by implementing a single mask grayscale lithography technique.

Ionomer Films Impact on The Structure, Flow Regime, and The Wettability of The Catalyst Layer of PEMFC

Percolation testing and contact angle measurements have been used to investigate the role of relative humidity on structure, mass transport, and wettability of a PEM fuel cell catalyst layer and membrane. Four samples were tested, two catalyst layers and two membranes. Structure and mass transport changes in the catalyst layers resulting from RH changes were studied in terms of percolation pressure. A clear change in the structure between low and high RH conditioning was observed. Relative humidity (RH) cycling also impacted percolation pressures with an indication of catalyst layer cracking. In addition, RH effect on wettability of both catalyst layers and membranes was studied by measuring contact angles of sessile drops.

Biobased Terpene Derivatives: Stiff and Biocompatible Compounds to Tune Biodegradability and Properties of Poly(butylene succinate)

Different copolymers incorporating terpene oxide units (e.g., limonene oxide) have been evaluated considering thermal properties, degradability, and biocompatibility. Thus, polycarbonates and polyesters derived from aromatic, monocyclic and bicyclic anhydrides have been considered. Furthermore, ring substitution with myrcene terpene has been evaluated. All polymers were amorphous when evaluated directly from synthesis. However, spherulites could be observed after the slow evaporation of diluted chloroform solutions of polylimonene carbonate, with all isopropene units possessing an R configuration. This feature was surprising considering the reported information that suggested only the racemic polymer was able to crystallize. All polymers were thermally stable and showed a dependence of the maximum degradation rate temperature (from 242 °C to 342 °C) with the type of terpene oxide. The graduation of glass transition temperatures (from 44 °C to 172 °C) was also observed, being higher than those corresponding to the unsubstituted polymers. The chain stiffness of the studied polymers hindered both hydrolytic and enzymatic degradation while a higher rate was detected when an oxidative medium was assayed (e.g., weight losses around 12% after 21 days of exposure). All samples were biocompatible according to the adhesion and proliferation tests performed with fibroblast cells. Hydrophobic and mechanically consistent films (i.e., contact angles between 90° and 110°) were obtained after the evaporation of chloroform from the solutions, having different ratios of the studied biobased polyterpenes and poly(butylene succinate) (PBS). The blend films were comparable in tensile modulus and tensile strength with the pure PBS (e.g., values of 330 MPa and 7 MPa were determined for samples incorporating 30 wt.% of poly(PA-LO), the copolyester derived from limonene oxide and phthalic anhydride. Blends were degradable, biocompatible and appropriate to produce oriented-pore and random-pore scaffolds via a thermally-induced phase separation (TIPS) method and using 1,4-dioxane as solvent. The best results were attained with the blend composed of 70 wt.% PBS and 30 wt.% poly(PA-LO). In summary, the studied biobased terpene derivatives showed promising properties to be used in a blended form for biomedical applications such as scaffolds for tissue engineering.

Columnar-structured thermal barrier coatings deposited via the water-based suspension plasma spray process

Suspension plasma spray (SPS) has been developed to be a rapid, facile and cost-effective process to deposit columnar-structured thermal barrier coatings (TBCs). Different than the most commonly used ethanol-based suspensions, water-based suspensions have not been used in the SPS process to deposit columnar-structured TBCs due to their high surface tension, although they are much cheaper and safer. In this work, a new water-based SPS process was prepared by adding surfactant to lower the surface tension. The optimum content of dispersant and surfactant added into the suspension was determined via the measurements of viscosity, particle size, surface tension, contact angles, and atomized droplet size. Coatings deposited using suspension with and without surfactant showed typical columnar-structured microstructures and vertically-cracked microstructures, respectively. The coatings deposited using suspension with surfactant also showed an evolution from columnar-structured microstructures to mixed microstructures of columns and cracks, and to homogeneous microstructures with the increase of standoff distance. The formation of different coating microstructures were correlated to the size of droplets after aerodynamic breakup and the Stokes number of in-flight particles. The new water-based suspension together with the water-based SPS process show high potential to be a cheap and effective alternative to the ethanol-based SPS process.

Superhydrophilicity of $\alpha$-Alumina Surfaces Results from Tight Binding of Interfacial Waters to Specific Aluminols

Understanding the microscopic driving force of water wetting is challenging and important for design of materials. In this work, we investigate, using classical molecular dynamics simulations, the water/$\alpha$-alumina (0001) and ($11\overline{2}0$) interfaces chosen for their chemical and physical differences. There is only one type of aluminol group on the nominally flat (0001) surface but three types on the microscopically rougher ($11\overline{2}0$) surface. We find that both surfaces are completely wet, consistent with contact angles of zero. Moreover, the work required to remove water from a nanoscale volume at the interface is larger for the (0001) surface than the ($11\overline{2}0$) surface, suggesting that the (0001) surface is more hydrophilic. In addition, translational and rotational dynamics of interfacial water molecules are slower than that in bulk water, suggesting tight binding to the surface. Interfacial waters show two major polar orientations, either pointing to or away from the solid surface. In the former case, waters donate strong hydrogen bonds to the surface, while in the latter they accept relatively weak ones from aluminol groups. The strength of hydrogen bonds is estimated using their lifetime and geometry. We found that for all aluminols, water-to-aluminol hydrogen bonds are stronger and have longer lifetimes than the aluminol-to-water ones. One exception is the long lifetime of the \ce{Al3OH}-water hydrogen bonds on the ($11\overline{2}0$) surface, due to geometric constraints. Interactions between surfaces and interfacial waters promote a templating effect whereby the latter are aligned in a pattern that follows the underlying lattice of the mineral surface.

Effect of Spontaneous and Water-Based Passivation on Components and Parameters of Ti6Al4V (ELI Grade) Surface Tension and Its Wettability by an Aqueous Solution of Sucrose Ester Surfactants

Solid wettability is especially important for biomaterials and implants in the context of microbial adhesion to their surfaces. This adhesion can be inhibited by changes in biomaterial surface roughness and/or its hydrophilic–hydrophobic balance. The surface hydrophilic–hydrophobic balance can be changed by the specifics of the surface treatment (proper conditions of surface preparation) or adsorption of different substances. From the practical point of view, in systems that include biomaterials and implants, the adsorption of compounds characterized by bacteriostatic or bactericidal properties is especially desirable. Substances that are able to change the surface properties of a given solid as a result of their adsorption and possess at least bacteriostatic properties include sucrose ester surfactants. Thus, in our studies the analysis of a specific surface treatment effect (proper passivation conditions) on a biomaterial alloy’s (Ti6Al4V ELI, Grade 23) properties was performed based on measurements of the contact angles of water, formamide and diiodomethane. In addition, the changes in the studied solid surface’s properties resulting from the sucrose monodecanoate (SMD) and sucrose monolaurate (SML) molecules’ adsorption at the solid–water interface were also analyzed. For the analysis, the values of the contact angles of aqueous solutions of SMD and SML were measured at 293 K, and the surface tensions of the aqueous solutions of studied surfactants measured earlier were tested. From the above-mentioned tests, it was found that water environment significantly influences the components and parameters of Ti6Al4V ELI’s surface tension. It also occurred that the addition of both SMD and SML to water (separately) caused a drop in the water contact angle on Ti6Al4V ELI’s surface. However, the sucrose monolaurate surfactant is characterized by a slightly better tendency towards adsorption at the solid–water interface in the studied system compared to sucrose monodecanoate. Additionally, based on the components and parameters of Ti6Al4V ELI’s surface tension calculated from the proper values of components and parameters of model liquids, it was possible to predict the wettability of Ti6Al4V ELI using the aqueous solutions of SMD and SML at various concentrations in the solution.