I agree with Kris and ScotM, but here are some additional observations. "Substitutional" is rather awkward and unusual, especially as both surrogate and substitute can be used as adjectives (surrogate parent, substitute teacher). Both can also be used as nouns. (Often words derived from Latin past participles, as both of these are, can be used as adjectives or nouns). But only substitute can be used as a verb. (Substitute, the verb, can be used transitively, as in "substitute the 2nd person plural for the first person singular in this sentence" OR intransitively, as in "I'm substituting for Amir when he has to miss class."). Etymologically, a substitute is "set up or established under" whereas the surrogate is the one "asked (to fulfil a function) over" -- if any difference in connotation arises from etymology, then, the surrogate would more likely be temporary and/or for a specific function only, while a substitute could be either temporary ("substitute teacher") or permanent ("we'll substitute a red widget when the black widget you ordered is sold out") and may remain in place for all possible functions. There might also be a connotation that a surrogate functions with the agreement or at the call of the person substituted, whereas a substitute need not have this connotation. (This latter hypothesis may explain why the questioner had an intuition that the surrogate was somehow more "voluntary.") "Replace" (verb) or "replacement" (noun or adjective) might span the meanings of both substitute and surrogate for some purposes.