Mass transport in binary TiO2:SiO2 and GeO2:SiO2 direct ink write glasses

The mass transport mechanisms of Ti in TiO2:SiO2 and Ge in GeO2:SiO2 direct ink write, additively manufactured glasses were studied. Due to the low solubility of Ti in SiO2 and high melting point of TiO2 relative to SiO2, Ti transport was found to occur via solid state interdiffusion between adjoining SiO2 and TiO2 precursor particles. The diffusivity of titanium in SiO2 measured over typical sintering temperatures (1000–1300°C) using Rutherford backscattering spectrometry was D=9.1×10−7[m2/s]exp(378[kJmol]RT)$D\ = \ 9.1{\rm{\ }} \times {10^{ - 7}}{\rm{\ }}[ {{\rm{m}}^2/{\rm{s}}} ]{\text{\ exp\ }}( {\frac{{378[ {\frac{{{\rm{kJ}}}{{{\rm{mol}}} ]}}{{RT}}} )$. This provides an estimate of ∼30 nm for the diffusion length under typical sintering conditions (2 h at 1200°C). Although Ti and Ge have similar diffusivities in SiO2 glass at low concentrations, GeO2 was found to be much more mobile during the sintering of printed GeO2:SiO2 green bodies. This was evident in glasses with phase separated GeO2 regions over length scales of ∼10 µm and in experiments involving binary xerogel films in which GeO2 migrated over ∼10 µm through cracked, porous SiO2 layers. Large phase separated regions and long transport lengths in GeO2:SiO2 suggest that the transport of GeO2 occurs prior to the densification of the SiO2 matrix via an alternative mechanism such as capillary flow. These results inform important considerations in the design of index modifying inks for the direct ink write process, namely initial precursor phase, mutual solubility with the base SiO2 glass, and mass transport throughout the sintering process.