Comb polymer architecture and particle size effects on the behavior of biphasic nanoparticle inks for direct-write assembly

Biphasic nanoparticle mixtures composed of attractive and repulsive colloidal species enable the direct-write assembly of 3D structures with much finer features than those produced by pure colloidal gels. These mixtures rely on the use of comb polymer dispersants to render one particle population stable, while the other population is attractive. In this thesis, we systematically investigate the effects of comb polymer architecture and particle size ratio on the behavior of biphasic nanoparticle inks with the overarching aim of further advancing the direct-write assembly of 3D colloidal structures.;We first investigated the effects of both pure polyelectrolytes, poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA), and comb polymer dispersants composed of a PMAA backbone with methoxy-poly(ethylene oxide) (mPEO) teeth of varying molecular weights on the stability of barium titanate (BaTiO 3) suspensions. While each dispersant imparts stability to BaTiO 3 nanoparticles at low ionic strength (< 0.01 M), only the PMAA-mPEO comb polymer with the longest teeth (MWteeth = 2000) provides stability at higher ionic strengths over a broad range of particle sizes and counterion valencies. These results provide guidelines for tailoring the molecular architecture and functionality of comb polymer dispersants for optimal stabilization of the repulsive particle population within the biphasic inks.;Next, particle size effects on the rheological properties of biphasic nanoparticle suspensions are studied. Shear elastic modulus, shear yield stress, and compressive yield stress are measured for mixtures of varying total volume fraction, attractive-to-repulsive volume fraction, and particle size ratio between attractive and repulsive species. Our observations indicate that the repulsive particles hinder the formation of the attractive gel network. The time required for shear elastic modulus to approach a steady-state value increases with the fraction of repulsive species. Furthermore, this behavior becomes more significant with increasing the repulsive particle size. Additionally, we find that biphasic suspensions composed of both identical and different mean particle sizes exhibit larger &phis;-scaling exponents for compressive yield stress than shear yield stress, indicating that such systems become more resistant to compression with increasing &phis;. This observation suggests that the biphasic suspensions flowing through fine nozzles are more resistant to filter pressing. Our findings provide new insights into controlling rheological properties of suspensions, which are applicable to a broad range of colloidal processing techniques.;Finally, the printing behavior of biphasic nanoparticle inks is investigated as a function of attractive-to-repulsive volume fraction and particle size ratio. Ink flow behavior is characterized by extrusion measurements, which reveals that the suspension viscosity, and, hence, pressure drop within micronozzles decrease as either the fraction or size of repulsive particles increases. We find that the shape retention of spanning filaments is improved by having a larger fraction of repulsive particles of smaller mean size, since this enhances the initial modulus recovery immediately after shear deformation. Biphasic inks composed of both identical and different mean particle sizes exhibit excellent flowability through fine nozzles compared to purely attractive inks, enabling fine-scale printing. These observations provide guidelines for optimizing the composition of biphasic inks for direct-write assembly of fine-scale, 3D structures.