Allegorithmic posts a great series that covers the texturing of a 3D character using the new Substance Designer 3, care of Kenny Lammers from Creative TD who shows the entire workflow and process of Substance Designer and how it can effectively make Photoshop seem like it is positively archaic for these types of tasks.
Over the the 11 or so videos in the series, you will get to see Substance designer in action, and also check out some of the new tools added to the recently released Substance Designer 3.
Check out the rest of the videos in this Substance Designer Character Texturing Tutorial series here.