Natural is a subset of Equi which is a subset of Theta.
If I use the = sign on a theta join is it exactly the same as just using a natural join???
Not necessarily, but it would be an Equi. Natural means you are matching on all similarly named columns, Equi just means you are using '=' exclusively (and not 'less than', like, etc)
This is pure academia though, you could work with relational databases for years and never hear anyone use these terms.