Thanks for the replies! The voltage doubler that Mike mentioned is exactly what I was talking about, although the matter of rectified DC being higher than the rms value of AC certainly plays its part too.
Thanks Mike, I hadn't considered the likely increase in ripple - good point! Possibly I need to think carefully about that. It may be that this places even more reliance on decent capacitors, and I was already wondering how much I'd really save over a new transformer, given the larger number of capacitors needed in a doubler anyway. Its encouraging that it worked for your valve amp though, so if I do have a go I'll post any conclusions on the forum for general interest,
cheers
Kevin