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Yep I can do that, do you mean install Windows on the SSD first, then reboot with the Live CD and copy the files from the old HDD straight to the new SSD?
The old HDD actually appears to be a mirrored RAID pair so I guess I should also test first whether I can mount one in Linux OK.
(An extra annoyance is that the situation has probably come about from owner's employer's helpdesk telling them to circumvent browser security settings to get their VPN working. I guess that calls for a VM for that sole purpose...?)
I'd boot into a Linux Live CD (or use a linux machine) and do it that way.