| Summary: | This study details the novel self-assembly of sodium titanate converted Ti-based microspheres into hierarchical porous 3D constructs, with macro-, micro-, and nanoporosity, for the first time. Ti6Al4V microspheres were suspended into 5 M NaOH (60 °C/24 h) solutions, with extensive variations in microsphere:solution ratios to modify microsphere interaction and initiate self-assembly through proximity merging of titanate surface dendritic growth. The formed structures, which either produced 1) unbonded, sodium titanate-converted microspheres; 2) flat (non-macroporous) scaffolds; or 3) open, hierarchically porous scaffolds, were then assessed in terms of their formation mechanism, chemical composition, porosity, as well as the effect of post-heat treatments on compressive mechanical properties. It was found that specific microsphere:solution ratios tended to form certain structures (<⅓ powder, 0.5 to 3 porous, >3 flat non-macroporous, >8 powder) due to a combination of microsphere freedom of movement, H2 gas bubble formation, and exposed surface reactivity. This promising discovery highlights the potential for lower temperature, simplistic production of 3D constructs with modifiable chemical properties due to the ion-exchange potential of titanate structures, with clear applications in a wide-range of fields, from medical materials to catalysts.
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