Thanks for getting back so quickly. I've been poking around in FAQs trying to find info on expansion vessels (without much luck, it has to be said!) I'll have another look tomorrow, and look at pressure relief valves too. Sounds plausible though. Could I have caused this whole problem by...
A few weekends ago I bled the radiators. Hadn't done it for a long time, and there was quite a lot of air in a couple of them. So I wasn't surprised when I had to let more water into the system to bring the pressure back up. But since then, the pressure's all over the place. Mostly it's too low...