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If you don't fully trust the internal protection of your micro-controller, you may use two diodes in series, as illustrated here
It is always useful to provide additional protection to the main device, but on this case in particular, any incremental voltage on 70v external terminals would produce a current limited to something about 2.1mA accross uC input, but on PIC family the inner clamp diodes supports forward currents up to ±20mA.
Zener has to conduct after it's avalanche region
My question is if any spark or vollt above 90v means ?
The 2nd table did not compute the "difference" value, as you did in 1st table.My readings are attached below with zener regulator and without zener diode.