Hey Dale,
It's a rusty lock washer, so go ahead and apply heat to your heart's content!
You definitely need the spacer, and I agree, the integral nut is just to hold things together while you reinstall the mud flap. Shouldn't really be necessary. I also think trying to 3D print a copy is going to way too much trouble. After all, when everything is back together, the only thing that can be seen is the head of the screw, and you have to get down on your hands and knees to even see that. So, improvise a spacer out of what ever you have laying around. In fact I think my idea of using one of those fat toothpaste tube caps is a good one! I might even think about doing it even though I have the original spacer, since as you say, it would prevent it from fusing together with the other hardware. You may have to add a washer to get the right thickness.
Since my spacer and the big washer were rusted together, the washer came out of it's space in the mud flap when I tried to unscrew things. I also needed heat to be able to unscrew the spacer from the screw. I then ran a tap through the nut on the spacer so it would go back together more easily. The spacer and large washer in my photo have been run through my tumbler for a few hours, then soaked in POR 15 Metal Prep for 30 minutes or so, and then coated with POR 15, so I should be good to go, especially since I never let water touch my car.
This thread is a whole lotta space devoted to such a small, relatively insignificant part!