Affine Deformation and Self-Assembly Alignment in Hydrogel Nanocomposites.

Tailoring the order in hierarchical structures is a key goal of bioinspired nanocomposite design. Recently, nacre-like materials have been developed by solvent evaporation methods that are scalable and attain advanced functionalities. However, understanding the alignment mechanisms of 2D fillers, nanosheets, or platelets remains challenging. This work explores possible pathways for nanocomposite ordering via orientation distribution functions. We demonstrate how the immobilization of 2D materials via (pseudo)network formation is crucial to alignment based on evaporation. We show a modified affine deformation model that describes such evaporative methods. In this, a gel network develops enough yield stress and uniformly deforms as drying proceeds, along with the immobilized particles, causing an in-plane orientation. Herein, we tested the dominance of this approach by using a thermo-reversible gel for rapid montmorillonite (MMT) particle fixation. We researched gelatin/MMT as a model system to investigate the effects of high loadings, orientational order, and aspect ratio. The nacre-like nanocomposites showed a semiconstant order parameter (⟨P2⟩ ∼ 0.7) over increasing nanofiller content up to 64 vol % filler. This remarkable alignment resulted in continuously improved mechanical and water vapor barrier properties over unusually large filler fractions. Some variations in stiffness and diffusion properties were observed, possibly correlated to the applied drying conditions of the hybrid hydrogels. The affine deformation strategy holds promise for developing next-generation advanced materials with tailored properties even at (very) high filler loadings. Furthermore, a gelling approach offers the advantages of simplicity and versatility in the formulation of the components, which is useful for large-scale fabrication methods.

Systematic Study of the Nanostructures of Exfoliated Polymer Nanocomposites.

High-performance bioinspired materials have shown rapid development over the last decade. Examples are brick-and-mortar hierarchical structures, which are often achieved via solvent evaporation. Although good properties are claimed, most systems are composed of stacked or intercalated platelets. Exfoliation is a crucial step to give ultimate anisotropic properties, e.g., thermal, mechanical, and barrier properties. We propose a general framework for all the various types of micro-scale structures that should be distinguished for 2D filler nanocomposites. In particular, the exfoliated state is systematically explored by the immobilization of montmorillonite platelets via (gelatin) hydrogelation. Scattering techniques were used to evaluate this strategy at the level of the particle dispersion and the regularity of spatial arrangement. The gelatin/montmorillonite exfoliated nanostructures are fully controlled by the filler volume fraction since the observed gallery d-spacings perfectly fall onto the predicted values. Surprisingly, X-ray analysis also revealed short- and quasi long-range arrangement of the montmorillonite clay at high loading.

The Glass Transition Temperature of Heterogeneous Biopolymer Systems.

Biopolymers are abundant, renewable, and biodegradable resources. However, bio-based materials often require toughening additives, like (co)polymers or small plasticizing molecules. Plasticization is monitored via the glass transition temperature versus diluent content. To describe this, several thermodynamic models exist; nevertheless, most expressions are phenomenological and lead to over-parametrization. They also fail to describe the influence of sample history and the degree of miscibility via structure-property relationships. We propose a new model to deal with semi-compatible systems: the generalized mean model, which can classify diluent segregation or partitioning. When the constant kGM is below unity, the addition of plasticizers has hardly any effect, and in some cases, even anti-plasticization is observed. On the other hand, when the kGM is above unity, the system is highly plasticized even for a small addition of the plasticizer compound, which indicates that the plasticizer locally has a higher concentration. To showcase the model, we studied Na-alginate films with increasing sizes of sugar alcohols. Our kGM analysis showed that blends have properties that depend on specific polymer interactions and morphological size effects. Finally, we also modeled other plasticized (bio)polymer systems from the literature, concluding that they all tend to have a heterogeneous nature.

Impact of nitrogen additions on soil microbial respiration and temperature sensitivity in native and agricultural ecosystems in the Brazilian Cerrado.

Soil microbial respiration (SMR1) is a major flux of CO2 from terrestrial ecosystems into the atmosphere, which depends on several abiotic factors, including soil temperature and nutrient availability. A nutrient of great interest in soil ecology is nitrogen (N) because of its use in agriculture and an expected increase of depositions in soils. Models on the relationship between SMR and temperature may be able to describe the effects of N addition on the temperature sensitivity of soil respiration (Q102). Hence, this study aimed to investigate the effects of N addition on SMR and Q10 values in soils of native Brazilian Cerrado (NC3), and of an agricultural ecosystem (AE4) cultivated over the past 17 years. SMR was stimulated by N additions (100 and 200 mg N kg dwt soil-1) in samples of Cerrado sites depending on the land use type and temperature assessed. The addition of 200 N kg dwt soil-1 to NC showed higher SMR values at 25 °C compared to soil without N input, whereas the same happened in AE at 30 °C. Overall, NC presented higher Q10 values than AE. N inputs increased Q10 in the Cerrado sites. In NC, the highest Q10 value occurred when 200 mg N kg dwt soil-1 was added to soil, whereas in AE the greatest value was observed for a lower dose (100 mg N kg dwt soil-1). This study shows that N additions to tropical soils alter Q10 values depending on dose and land use. These are important findings to compare the fragility of pristine and cultivated Brazilian Cerrado ecosystems in the perspective of climate change.