Here are the main suspects, Groupie.............
Small leak in the system somewhere (doesn't take much). Have a good look around, especially rad connections.
When the water heats up, it expands, and pressure goes up. To save the system from blowing up, an expansion vessel acts like a cushion to take up the extra pressure............ vessel diaphragm may be ruptured..... no cushioning, so the safety valve blows and the water escapes outside.
Safety valve (pressure relief valve) may be faulty, going off too soon.
Most likely by far though ............... pressure vessel has lost its charge of air pressure (on the other side of the diaphragm) ....... therefore diaphragm flops around with no cushioning effect.
The vessel should have a schrader valve sticking out of it (same as a tyre valve.) It just needs pumping up with a bicycle pump. Look in the manual for the pressure. Probably around 12 lbs/sq.inch. Heating engineers usually top this up at service time.