First of all the formal difference: While durchaus is an adverb (built from the concatenation of two prepositions), völlig is an adjective. From a formal viewpoint that means völlig can be replaced by durchaus when in adverbial use only (for example, when völlig modifies another adjective as in the following example).
Das ist völlig richtig
Das ist durchaus richtig
Note, however, the replacement modifies the meaning - The second example expects an "aber" (like in most cases when durchaus is used), while the first one doesn't necessarily.
When used as an adjective, the replacement doesn't really work:
Das ist völliger Blödsinn
Das ist durchaus Blödsinn ...
(The "durchaus" example is a valid sentence, but the meaning is entirely different: "völliger Blödsinn" is "complete nonsense", but the second example translates to something along the lines of )
While this may be nonsense, .....
I would rather state that sometimes (but, in most cases, not) durchaus and völlig can be synonyms.