Curently, in ff, pure character vectors are not implemented. Factors are. As c('a','b') is a character, it will not work to convert it to ff. But it is of course possible to convert factors to ff.
require(ff)
class(c('a', 'b'))
[1] "character"
class(factor(c('a', 'b')))
[1] "factor"
as.ff(factor(c('a', 'b')))
ff (open) integer length=2 (2) levels: a b
[1] [2]
a b
class(as.ff(factor(c('a', 'b'))))
[1] "ff_vector" "ff"
Mark also that the factor levels are in RAM. All the rest is on disk.