In recent years, advancements in additive manufacturing (AM) technologies have paved the way for 3D-printed flexible hybrid electronics (FHE) and created opportunities for extending these gains to RF applications. However, printed metal interconnects and devices are typically characterized by high porosity and chemical impurities that significantly limit their electrical conductivity and RF performance compared to bulk equivalents. Using direct ink writing (DIW), two silver inks, a nanoflake suspension and a nanoparticle-reactive ink, were investigated to understand the relationship between free interfacial energy, sintering behavior, DC conductivity, and RF loss. The printed silver samples were characterized using scanning electron microscopy, x-ray diffraction, and x-ray photoelectron spectroscopy to monitor microstructural evolution, grain size and orientation, and chemical purity as a function of heat treatment temperature. Three heat treatments were applied to each ink: the manufacturer's recommendation, 225°C for 30 minutes, and 350°C for 30 minutes. Four-wire structures and coplanar waveguides were printed to compare the DC and RF performance up to 18 GHz, respectively. The results show that ink formulations that facilitate larger grains, high density, and good chemical purity have superior RF performance. A low resistivity of 1.4 times bulk Ag, average of 0.8% greater RF loss factor than evaporated Ag, and a maximum current density of 4.6 x 105 A/cm2 were achieved with printed structures. This work highlights the importance of engineering a high density and high purity microstructure in printed silver components necessary for high-performance printed electronics.