OK, they are normally closed zone valves with an auxiliary switch. When you apply voltage to the brown and blue wires the valve opens and the auxiliary switch closes, connecting the grey and orange wires. The grey is usually connected to a permanent 240 supply; the orange goes to the boiler switched live terminal.the model numbers are V4043H1106 for the airing cupboard one and 272848 for the ones in the loft.
Edit: Some version of this valve have a white wire as well. This is not used in your set-up.
However we still have the strange problem with your voltages on the thermostat. I haven't worked out what is happening yet; will get back to you.