Higher contact angles or amplified wettability observed on surfaces of rough solid materials are typically expressed as a function of a physical dimension (roughness factor). Herein, we present a simple experimental approach that demonstrates that roughness may only magnify the inherent surface chemistry that seems to have direct influence on surface wettability. We investigate gradual change in surface chemistry (hydrophobisation) of rough and smooth glass surfaces, from a very low concentration (10⁻⁷ M) of dichlorodimethylsilane, DCDMS through various intermediate hydrophilic/hydrophobic states to when the surfaces are maximally hydrophobised with DCDMS at 0.1 M. The wettability of the modified glasses was studied by water contact angle measurements using drop shape analysis system (DSA). The data obtained indicate a deviation from Wenzel model, with the functionalized rough glass surfaces showing higher reactivity towards DCDMS when compared to the smooth glass surfaces, indicating that the two surfaces are not chemically identical. Our study reveals that just like transforming a solid material to powder, a well-divided glass (rough) surface may not only exhibit a greater surface area than the smooth counterpart as rightly predicted by the Wenzel model, but seems to be bloated with functional groups (–OH or –CH₃) that can amplify surface interaction when such functional species dominate the solid surface.

The high demand for lithium (Li) relates to clean, renewable storage devices and the advent of electric vehicles (EVs). The extraction of Li ions from aqueous media calls for efficient adsorbent materials with various characteristics, such as good adsorption capacity, good selectivity, easy isolation of the Li-loaded adsorbents, and good recovery of the adsorbed Li ions. The widespread use of metal-based adsorbent materials for Li ions extraction relates to various factors: (i) the ease of preparation via inexpensive and facile templation techniques, (ii) excellent selectivity for Li ions in a matrix, (iii) high recovery of the adsorbed ions, and (iv) good cycling performance of the adsorbents. However, the use of nano-sized metal-based Lithium-ion sieves (LISs) is limited due to challenges associated with isolating the loaded adsorbent material from the aqueous media. The adsorbent granulation process employing various binding agents (e.g., biopolymers, synthetic polymers, and inorganic materials) affords composite functional particles with modified morphological and surface properties that support easy isolation from the aqueous phase upon adsorption of Li ions. Biomaterials (e.g., chitosan, cellulose, alginate, and agar) are of particular interest because their structural diversity renders them amenable to coordination interactions with metal-based LISs to form three-dimensional bio-composite materials. The current review highlights recent progress in the use of biopolymer binding agents for the granulation of metal-based LISs, along with various crosslinking strategies employed to improve the mechanical stability of the granules. The study reviews the effects of granulation and crosslinking on adsorption capacity, selectivity, isolation, recovery, cycling performance, and the stability of the LISs. Adsorbent granulation using biopolymer binders has been reported to modify the uptake properties of the resulting composite materials to varying degrees in accordance with the surface and textural properties of the binding agent. The review further highlights the importance of granulation and crosslinking for improving the extraction process of Li ions from aqueous media. This review contributes to manifold areas related to industrial application of LISs, as follows: (1) to highlight recent progress in the granulation and crosslinking of metal-based adsorbents for Li ions recovery, (2) to highlight the advantages, challenges, and knowledge gaps of using biopolymer-based binders for granulation of LISs, and finally, (3) to catalyze further research interest into the use of biopolymer binders and various crosslinking strategies to engineer functional composite materials for application in Li extraction industry. Properly engineered extractants for Li ions are expected to offer various cost benefits in terms of capital expenditure, percent Li recovery, and reduced environmental footprint.

Pickering emulsions, with anisotropic droplets, are often prepared via methods that involve long procedures or require elevated temperatures, exotic particles and equipment, thereby limiting their industrial applications. Herein, we report a facile method for preparing anisotropic Pickering emulsion droplets which does not require elevated temperatures, exotic particles and equipment. This method involves measuring 7 cm³ of different concentrations of aqueous NaCl solution (0 to 1000 mM) into separate screw cap glass vials, adding 4 wt.% rod- or cube-shaped CaCO₃ particles, followed by 7 cm³ of vegetable oil. The salt solution-particle-oil mixtures are then sheared at 13000 rpm for 3 min. It was found that mixtures containing the cube-shaped CaCO₃ particles formed oil-in-water emulsions with anisotropic droplets (length ≤ 2430 μm) while those containing the rod-shaped ones formed emulsions with isotropic droplets (diameter ≤ 800 μm). The results also revealed that the aspect ratio of the anisotropic droplets is between 2.7 to 3.3, depending on NaCl concentration. In addition, the fraction of aqueous and oil phases resolved for three years is within 0.2 to 0.6 and ≪ 0.1, respectively, depending on NaCl concentration. Zeta potential measurement shows a decrease in the magnitude of particle charge with increasing salt concentration: a strong decrease for mixtures with cube-shaped CaCO₃ particles and a weak decrease for mixtures with the rod-shaped ones. Graphical Abstract

The high demand for lithium (Li) relates to clean renewable storage devices and the advent of electric vehicles (EVs). The extraction of Li ions from aqueous media calls for efficient adsorbent materials with various characteristics, such as good adsorption capacity, good selectivity, easy isolation of the Li-loaded adsorbent, and good recovery of the adsorbed Li ions. The widespread use of metal-based adsorbent materials for Li ions extraction relates to various factors: (i) the ease of preparation via inexpensive and facile templation techniques, (ii) excellent selectivity for Li ions in a matrix, (iii) high recovery of the adsorbed ions, and (iv) good cycling performance of the adsorbents. However, the use of nano-sized metal-based LISs is limited due to challenges associated with isolating the loaded adsorbent material from the aqueous media. Adsorbent granulation process employing various binding agents (e.g., biopolymers, synthetic polymers, and inorganic materials) affords functional particles with modified morphological and surface properties that support easy isolation from the aqueous phase upon adsorption of Li ions. Biomaterials (e.g., chitosan, cellulose, alginate, and agar) are of particular interest because their structural diversity renders them amenable to coordination interactions with metal-based LISs to form 3D microcapsules. The current review highlights recent progress in the use of biopolymer binding agents for the granulation of metal-based LISs, along with various crosslinking strategies employed to improve the mechanical stability of the granules. The study reviews the effects of granulation and crosslinking on adsorption capacity, selectivity, isolation, recovery, cycling performance and the stability of the LISs. Adsorbent granulation using biopolymer binders has been reported to modify the uptake properties of the bio-adsorbent materials to varying degrees, in accordance with the surface and textural properties of the binding agent. The review further highlights the importance of granulation and crosslinking for improving the extraction process of Li ions from aqueous media. This review contributes to manifold areas related to industrial application of LISs, as follows: 1) to highlight recent progress in the granulation and crosslinking of metal-based adsorbents for Li ions recovery, 2) to highlight the advantages, challenges, and knowledge gaps of using biopolymer-based binders for granulation of LISs, and finally, 3) to catalyze further research interest into the use of biopolymer binders and various crosslinking strategies to engineer functional adsorbent materials for application in Li extraction industry. Properly engineered extractants for Li ions are expected to offer various cost benefits in terms of capital expenditure, percent Li recovery, and reduced environmental footprint.

Coating porosity is an important property that supports solid-gas and solid-liquid exchange that can either enhance various science and technological applications or promote damage if not properly controlled. However, non-destructive instrumental techniques for the measurement of porosity on coated walls or surfaces can be quite challenging. Here, a seamless capillary rise technique has been used to determine both the thickness and porosity of a thin silica coating. Uniform coatings were prepared from 5 wt% hydrophobic fumed silica in absolute ethanol and spin-coated at 500–8000 rpm on glass slides. Capillary imbibition of squalane was then controlled into known areas of the resulted hydrophobic nano-porous coatings. The mass of the solid (silica) and the infiltrated oil (squalane) were gravimetrically measured. The porosity of the material was calculated as the percentage fraction of the pore volume while the film thickness was determined as the ratio of the total volume to the area of coverage. Mean values of the porosity and coating thickness calculated from capillary impregnation technique were 86 ± 2% and 3.7 ± 0.2 μm, respectively. The coating thickness obtained was comparable with those revealed by SEM and Dektak profiler measurements. This study highlights the effectiveness of capillary rise as a simple and cost-effective non-destructive technique for assessment of coating thickness and porosity.