A highly ordered alginate/montmorillonite bionanocomposite structure is presented. The alignment of the bionanocomposites has been determined by environmental scanning electron microscopy (ESEM) and wide-angle X-ray scattering (WAXS). The ESEM micrographs show a high inplane orientation of the bionanocomposite, while 2D X-ray scattering images show a clear angle dependency that confirms preferential orientation of montmorillonite (MMT) platelets. The order parameter (⟨P 2 ⟩) was calculated from azimuthal intensity profiles derived from WAXS measured over the MMT 001 reflection, using the Maier−Saupe and the affine deformation model. We observe that the ⟨P 2 ⟩ values depend on the MMT concentration, which is explained by the MMT− alginate interaction. We propose an affine deformation model based on gel formation achieved by alginate adsorption on the edges of MMT, which develops yield stress and deforms the MMT platelets during drying resulting in high range ⟨P 2 ⟩ values.

The promise of crystal composites with direction-specific properties is an attractive prospect for diverse applications; however, synthetic strategies for realizing such composites remain elusive. Here, we demonstrate that anisotropic agarose gel networks can mechanically “mold” calcite crystal growth, yielding anisotropically structured, single-crystal composites. Drying and rehydration of agarose gel films result in the affine deformation of their fibrous networks to yield fiber alignment parallel to the drying plane. Precipitation of calcium carbonate within these anisotropic networks results in the formation of calcite crystal composite disks oriented parallel to the fibers. The morphology of the disks, revealed by nanocomputed tomography imaging, evolves with time and can be described by linear-elastic fracture mechanics theory, which depends on the ratio between the length of the crystal and the elastoadhesive length of the gel. Precipitation of calcite in uniaxially deformed agarose gel cylinders results in the formation of rice-grain-shaped crystals, suggesting the broad applicability of the approach. These results demonstrate how the anisotropy of compliant networks can translate into the desired crystal composite morphologies. This work highlights the important role organic matrices can play in mechanically “molding” biominerals and provides an exciting platform for fabricating crystal composites with direction-specific and emergent functional properties.

Chemical cleaning is routinely performed in reverse osmosis (RO) plants for the regeneration of RO membranes that suffer from biofouling problems. The potential of urea as a chaotropic agent to enhance the solubilization of biofilm proteins has been reported briefly in the literature. In this paper the efficiency of urea cleaning for RO membrane systems has been compared to conventionally applied acid/alkali treatment. Preliminary assessment confirmed that urea did not damage the RO polyamide membranes and that the membrane cleaning efficiency increased with increasing concentrations of urea and temperature. Accelerated biofilm formation was carried out in membrane fouling simulators which were subsequently cleaned with (i) 0.01M sodium hydroxide (NaOH) and 0.1M hydrochloric acid (HCl) (typically applied in industry), (ii) urea (CO(NH 2 ) 2 ) and hydrochloric acid, or (iii) urea only (1340 g/L water ). The pressure drop over the flow channel was used to evaluate the efficiency of the applied chemical cleanings. Biomass removal was evaluated by measuring chemical oxygen demand (COD), adenosine triphosphate (ATP), protein, and carbohydrate content from the membrane and spacer surfaces after cleaning. In addition to protein and carbohydrate quantification of the extracellular polymeric substances (EPS), fluorescence excitation−emission matrix (FEEM) spectroscopy was used to distinguish the difference in organic matter of the remaining biomass to assess biofilm solubilization efficacy of the different cleaning agents. Results indicated that two-stage CO(NH 2 ) 2 /HCl cleaning was as effective as cleaning with NaOH/HCl in terms of restoring the feed channel pressure drop (>70% pressure drop decrease). One-stage cleaning with urea only was not as effective indicating the importance of the second-stage low pH acid cleaning in weakening the biofilm matrix. All three chemical cleaning protocols were equally effective in reducing the concentration of predominant EPS components protein and carbohydrate (>50% reduction in concentrations). However, urea-based cleaning strategies were more effective in solubilizing protein-like matter and tyrosine-containing proteins. Furthermore, ATP measurements showed that biomass inactivation was up to two-fold greater after treatment with urea-based chemical cleanings compared to the conventional acid/alkali treatment. The applicability of urea as an alternative, economical, eco-friendly and effective chemical cleaning agent for the control of biological fouling was successfully demonstrated.

The water sorption and diffusion in (reduced) graphene oxide‐alginate composites of various compositions is analyzed. Water sorption of sodium alginate can be significantly reduced by the inclusion of graphene oxide sheets due to the formation of an extensive hydrogen bonding network between oxygenated groups. Crosslinking alginate with divalent metal ions and the presence of reduced graphene oxide can further improve the swelling resistance due to the strong interactions between metal ions, alginate, and filler sheets. Depending on conditions and composition, the overall water barrier properties of alginate composites improve upon (reduced) graphene oxide filling, making them attractive for moisture barrier coating applications. Water sorption kinetics in all alginate composites indicate a non‐Fickian diffusion process that can be accurately described by the Variable Surface Concentration model. In addition, the water barrier properties of sodium alginate‐graphene oxide composites can be adequately predicted using a simple model that takes the orientational order of filler sheets and their effective aspect ratio into account.

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