The effect of solidification direction with respect to gravity on ice-templated TiO2 micro-structures

TL;DR

This study examines how the direction of solidification relative to gravity influences the microstructure of ice-templated TiO2, revealing buoyancy-driven fluid flow effects during upward solidification that affect pore orientation and defect formation.

Contribution

It provides new insights into the role of buoyancy-driven convection in ice-templating, highlighting the importance of solidification direction on microstructural features.

Findings

Buoyancy-driven fluid flow occurs during upward solidification.

Upward solidification causes pore tilting and defects.

Downward and horizontal solidification show no such features.

Abstract

Ice-templating produces materials with aligned, elongated pores via directional solidification of particle suspensions, sublimation of the solidified fluid, and sintering of the particle walls. Most ice-templating studies utilize upward solidification techniques, where solid ice is located at the bottom of the solidification mold, the liquid suspension is on top of the ice, and the solidification front advances upward, against gravity. Liquid water reaches its maximum density at 4{\deg}C; thus, liquid nearest the cold source is less dense than warmer liquid above. The lower density liquid nearest the cold source is expected to rise due to buoyancy, promoting convective fluid motion during solidification. Here, we investigate the effect of solidification direction with respect to the direction of gravity on ice-templated microstructures to study the role of buoyancy-driven fluid motion during solidification. We hypothesize that, for upward solidification, the convective fluid motion that results from a liquid density gradient occurs near the solidification front. For downward solidification, we expect that this fluid motion occurs farther away from the solidification front. Aqueous suspensions of TiO2 nanoparticles are solidified upward (against gravity, with ice on bottom and water on top), downward (water on bottom, ice on top), and horizontally (perpendicular to gravity). Microstructural investigation of sintered samples shows evidence of buoyancy-driven, convective fluid flow during solidification for samples solidified upwards (against gravity), including tilting of the wall (and pore) orientation with respect to the induced temperature gradient, ice lens defects, and radial macrosegregation. These features are not observed for downward nor horizontal solidification configurations.