Sorted - the heat exchanger was well and truly sooted up. It can't have been serviced in years. The chap told us that the boiler does indeed probably only have a year or two left in it, so that's large bill to look forward to!
Cheers all
Thanks all for your replies. Got someone coming round on Wed (these things pick their moment!). He did say it could be a blocked heat exchanger. We've only been in the house a few months and haven't put monoxide alarms in yet, just shows it's not a thing to neglect.
When my CH boiler comes on, it behaves normally for about 17 secs. Then the flames turn orange and - most alarmingly - spread out much further than they are meant to go, the flames spilling outside the boiler casing. The boiler is a Vaillant VCW T3W, on which the pilot is not glassed in. I've...