Just noticed you've not had a reply for this.
I'm not expert on Freud (though did visit the museum in Vienna this year). As I understand it, free association probably covers most of it, though it possibly could have been a form of semi-structured interview - as he would have had areas he'd been keen to explore and might have asked specific questions.
Googling it will probably give a suitable answer - his methods aren't especially robust by modern standards, so unless this is a specific question for a specific piece of work, I wouldn't worry too much about it.