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DESIGN, ASSEMBLY AND CHARACTERIZATION OF COMPOSITE ...

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The combined use of PAA and PAA-90K for BT ink preparation serves two<br />

purposes. First, at φsolids=0.43, the BT gel prepared with only lower molecular weight<br />

PAA lacks sufficient elasticity to form self supporting structures. By supplementing<br />

higher molecular weight PAA-90K as a fraction of the total dispersant, the barium<br />

titanate ink has sufficient elasticity at φsolids=0.43 without unduly increasing viscosity. 109,<br />

110 The short chain dispersant (Darvan 821A) is thought to adsorb tightly to the BT<br />

surface, whereas the PAA-90K may form a more extended polymer brush that enhances<br />

interaction with the PEI flocculant molecules. Second, PAA-90K seems to reduce the<br />

drying shrinkage difference between the BT ink and the Ni(m) composite ink. All these<br />

inks may be extruded through 200 µm diameter nozzle consistently without clogging.<br />

5.3.2. Rheological Characterization<br />

The Ni(m) inks with various BT:Ni ratios demonstrate similar aqueous colloidal<br />

gel behaviors at φsolids=0.43 (see Figure 5.4) and are comparable to ceramic colloidal gels<br />

used in Robocasting. Shear elastic modulus and yield stress of a colloidal gel depends on<br />

several factors, including solid volume fraction, shear modulus of particles, and the<br />

strength, stiffness and density of inter-particle bonds. For Ni(m) inks, the measured shear<br />

elastic moduli range from G'=160kPa for BT:Ni=4:1 to G ' =280 kPa for BT:Ni=1:4. Fro<br />

comparison, the BT ink has a measured shear elastic modulus of 99kPa. The difference<br />

in G' can likely be attributed to the relatively stiffer interparticle bonds formed during<br />

heteroflocculation compared to simple bridging flocculation of BT gels with PEI addition.<br />

147

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