@ Xeim: Speak of the devil, I'm back.
Two methods have been shown for forcing Shinigami/Hollow hybrids: Urahara’s Hogyoku and Aizen’s currently unknown method.
Ichigo is unique in that he is a “natural” Vizard. During his transformation into a Hollow, he awakened his dormant Shinigami powers, resulting in a hybrid. It is unknown if this was deliberately orchestrated by Urahara or a fortunate accident.
The other Vizards are resultant from Aizen’s method forcing a Hollow transformation on shinigami and Urahara trying to fix them with the Hogyoku, resulting in hybrids.
Each sentient Hollow is unique in appearance. But it is interesting to note that once a Hollow reaches Adjucha class, it is almost invariably covered in the same plaster-like material as the Hollow mask. When Arrancar release their zanpakuto, the resulting transformation is typically covered in this material as well. When Ichigo briefly changes into a full Hollow, his Hollow body is covered in this material.
Aizen’s method of befriending, creating, and experimenting on Hollows pre-Hogyoku/defection is currently unknown.
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