Thanks for the replies.
If ordinary silicone is successful then I think I’ll go for a heat resistant flue block type, geocell do one available at toolstation that should do the job.
Though it’s an excellent idea expanding the pipe isn’t that practical in my case as the exhaust outlets in the head have worn unevenly so the pipes would have to be expanded to suit the hole. And unless the pipes were a fairly snug and tight fit some sort of sealant would still have to be used.
I did consider drilling and tapping holes round the outer edge of the exhaust outlet, so a ring clamped to the pipe could bolt up to the head, I think Unity Equipe sell something similar. However in my opinion the wall thickness on the head isn’t substantial enough to allow a thread of a useful size to be tapped in it.