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Bio-based compostable starch aerogels have significant potential as a sustainable alternative to traditional polymer aerogels across various applications. However, they suffer from very significant shrinkage, shown in published work as 40–50% using existing processes. We hypothesized that the shrinkage is largely caused by pore collapse through the solvent exchange process, during which the water used to fabricate the starch matrix is replaced with ethanol. To mitigate this issue, this work introduces two strategies: (1) implementing a deep-freezing protocol (DFP) prior to the solvent exchange, followed by pure ethanol solvent exchanges instead of water/ethanol mixtures, and (2) incorporating chitin as a structural additive. As a baseline, we fabricated potato starch aerogels (PSAs) using conventional processes of mixing, heating, and retrogradation. By applying a DFP before pure ethanol exchanges, shrinkage was reduced from 44% to 10% in pure PSA samples. Furthermore, the addition of chitin reduced shrinkage to 8% in potato starch-chitin aerogels. Porosity, density, surface area, pore size distribution, thermal decomposition temperature, thermal conductivities, and scanning electron microscopy images demonstrate a correlation between reduced shrinkage and desired thermal material properties.
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Structural Formation and Pore Control of Freeze-Cast Directional Graphene Aerogel (DGA)
Directional graphene aerogels (DGAs) are proposed as electrode materials to alleviate ionic and mass transport issues in organic redox flow batteries (ORFBs). DGAs with high pore directionality would provide low resistance channels for effective ionic charge and liquid electrolyte transport in these devices. DGAs’ porous and directional characteristics can be controlled by the growth of ice crystals during freeze casting, which is influenced by the self-diffusivity of water, phase change driving forces, water−ice graphene interactions, and convection in the water−graphene media. It is found that mass transport-related properties of DGAs, including pore size and directionality, show a significant dependence on freezing temperature, graphene oxide (GO) loadings, and synthesis vessel diameter-to-height ratio (D/H). For the freezing temperature change from −20 to −115 °C, the average pore size progressively decreased from 120 to 20 μm, and the pore directionality transitioned from lamellar to ill-defined structures. When GO loadings were increased from 2 to 10 mg/mL at a fixed freezing temperature, pore size reduction was observed with less defined directionality. Furthermore, the pore directionality diminished with an increased width-to-height aspect ratio of DGA samples due to the buoyancy-driven convective circulation, which interfered with the directional ice/pore growth. Understanding the comprehensive effects of these mechanisms enables the controlled growth of ice crystals, leading to graphene aerogels with highly directional microstructures.
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- Award ID(s):
- 1933800
- PAR ID:
- 10492643
- Publisher / Repository:
- ACS Publications
- Date Published:
- Journal Name:
- ACS Applied Materials & Interfaces
- Volume:
- 16
- Issue:
- 1
- ISSN:
- 1944-8244
- Page Range / eLocation ID:
- 425-434
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acsami.3c10998
