Would this have been possible without PIO?
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In a sense the PIO is a bit 'cheaty' when claiming "bit-banging", because the PIO is the ultimate peripheral, programmable to be whatever you need. It's no mean feat to make the PIO do the sorts of things happening here, by any stretch, but "bit-banging" typically means using the CPU to work around the lack of a particular peripheral.
From that perspective, there's precious few µCs out there that could bit-bang 100MBit/s Ethernet - I'm no expert, but I _think_ that's a 125MHz IO clock, so if you want 4 CPU cycles per transition to load data and push it onto pins, you're looking for a 500MHz µC, and at those speeds you definitely have to worry about the bus characteristics, stalls, caching, and all those fun bits; it's not your old 8-bit CPU bit-banging a slow serial protocol over the parallel port any more.