Looking back at all the posts in this thread, I don't think that you've ever said what type of control system is in place - how many zones valves there are and whether it/they are the 2-port or 3-port type.
Going by the age of the system and by your assertion that the valve doesn't use microswitches, my hunch is that you have a W-Plan system which has a single 3-port diverter valve. See
In the event of an air lock in the HW circuit which prevented the cylinder from getting hot (unlikely) the stat would never be satisfied, so the radiators wouldn't be heated either.
Assuming my hunch about it being a W-Plan system is correct, if the radiators get hot but the cylinder doesn't, either the wet part of the valve is stuck in the CH position, or the cylinder stat is telling the valve that the HW is hot when it isn't. This could be a wiring problem - but unlikely if it worked in the past and the wiring has not been disturbed, or maybe the stat's contacts could have welded themselves closed so that it is always "satisfied" even when the water is cold.
If you don't think it's a W-Plan system, please tell us what it actually is.