Casualty was originally shot 50i, and for a brief period a horrible 25p 'film effect' was added in post. This was a really early version (I think it was something like 75% field drop/25% field blend in a low-resolution Charisma DVE - not the decent quality ARC100/ARC110 or Alchemist processing that followed. It looked dreadful.) After a brief period the show returned to 50i and continued that way for a long time.
It then switched to 25p and this may have co-incided with the switch from SD to HD - but it certainly has been 25p for a good long time.
I don't think Casualty has ever been shot on film. Even in the early days in the 80s, the location stuff was shot on video I think.
As for iPlayer, on some platforms there are now 1280x720/50p and 960x540/50p profiles, which are deinterlaced 50i with full motion, so these days iPlayer CAN deliver fluid motion on shows shot 50i natively (Entertainment, Sport and most other studio-based shows). Not all platforms yet receive these profiles (my Sony UHD Connected Red Button set was still stuck at 25p last time I checked, but my PC, my Chromecast - with the right settings adjustment - and my Apple TV 4 all happily run the 50p profiles)