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If this is something new and you have changed nothing until now, the possiblities are limited.
1) blockage of the radiator
2) stuck Theromstat (replaced)
3) air in system(how'd it get there, boiling?)unlikely
4) clogged exterior of the radiator/AC condenser (look in between the 2 units for blockage) but makes sense because the AC fans don't cool down the temp at all
5) Blown Head Gasket (likely) I've had this happen and the symptoms are similar and you blew a hose from excess pressure
6) Dead water pump (without leakage, questionable)
If I had to guess in order from most likely:
#5, 6, 4
drcoffee, your scaring me. Even though you described good symptoms.
Started to drive today, cruised at about 190-198, 3miles. . Stopped for 15 minutes.
Started to drive, was at 192 and went as high as 226, turned on AC, cooled to 214 and stayed there for 1/2 mile. Parked it, it's not boiling over, hoses have no pressure, feel spongy (normal). Will let cool down, then go for a longer freeway cruise. I think, (hoping) it just had air trapped and is now better. Temp today is about 98 for the high. :(
Stock, the C5 runs hot normal above 200*. In hot climates a hi-cap radiator like Dewitts is required plus a 180* or lower t-stat. With fans set around 180* the LS1 will run smoother and output a few more HP. As LG said the other day, max HP is 180-190*. Plus it will keep A4 temps below 200* to extend tranny life.