OK managed to measure voltages (All AC voltages) this evening :)
HW + CW Both on (Boiler On). Orange = 240V, White = 240V, Grey = 0V
HW Only On. (Boiler On) Orange = 240V, White = 28V, Grey = 0V
CH Only On (Boiler off??). Orange = 0V, White = 240V, Grey = 15V