Got the same problem. CH guy changed the Pressure relief valve ( which was leaking) first £ 10 parts and then changed the expansion vessel £42 parts, labour extra.
Apparently there is a rubber diaphragm in the expansion vessel that goes porous and leaks.Throw all the pressures haywire. Pressure builds up to 3 bar and then overflows, loses pressure after a couple of hours and can't reignite. Job easy to do 1.5 hours approx.
Just been fixed. Tell you tomorrow if it works. CH engineer is confident it will be OK.
Bob Wild, December 2009