Mais il me faut quelques volontaires bien décidés.
in that sentence, décidés is considered as an adjective right? So does the phrase bien décidés an adjectival phrase or adverbial phrase?
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The phrase "bien décidés" qualifies "quelques volontaires", which is a noun phrase, as its head is the noun "volontaires".
A phrase that qualifies a noun phrase would typically be an adjectival phrase: this is, similarly to the noun phrase, because its head is the adjective "décidés" (a past participle used as an adjective). The fact that "bien", which in turn qualifies "décidés", is an adverb doesn't change the natural of the phrase.
So, "bien décidés" is an adjectival phrase that depends on the noun phrase "quelques volontaires". Since it's dependent on it, if you take the larger phrase "quelques volontaires bien décidés", that is also a noun phrase.
They are separate words belonging to different syntactic classes. "bien" is an adverb here that determines the adjective "décidés". "bien" can be substituted for another adverb as "très".
"bien" can be an adjective also, then it could be possible to consider that "bien décidé" could be an adjectival phrase as "bien portant". But, in your case, they don't form a phrase (according to the French terminology "locution"). An adverbial phrase with the word "bien" might be "particulièrement bien", "fort bien", "bien entendu" for example.
But if you are looking for the dependency between the words, then you are considering the word "phrase" as the equivalent of the French word "syntagme", in that case, "bien décidé" is an adjectival phrase.