I had exactly the same problem, it turned out to be the expansion vessel(the internal diaphram had gone) to test, put a tyre pressure guage on the vessel, it should be about 18psi ish, it is situated at the very back at the top behind the flue. remove the plastic cap (same as a car tyre) press the centre and let a bit of air out...if nothing comes out charge it and try again but if any water comes out the diaphram has gone.
A new expansion vessel was about £60 and a pig to fit, a plumber mate said it can be done fastened to the wall. I couldnt, it had to come off...
Hope its of some help.
Fletch
Mick Fletcher, December 2007