out of curiousity i bled all the radiators and rail today to see if there was any air in the system (none as far as i could tell as the water dribbled out almost immediately) and checked the lockshield screws on all the rads, all open about 1.5 turns apart, broke a key doing it, the bleed screws were tight!
£300 of parts/labour and no further ahead.... how much is a new boiler?
just to hopefully close the story on this, i got another engineer in shook who his head in disbelief at all the parts that had been fitted, pointed to the (closed) gate valve and said that it should be open otherwise there is nowhere for the water to escape to which is why it's overheating.... no need for any of those parts to have been replaced he reckoned 10 minute check and a turn of the hand was all it needed and fingers crossed it's been fine since!
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