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are we only talking about quattros only or FWD too?
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Even more so FWD!
On a quattro you need the rears to give a little to enable them to provide drive...a sliding rear end isn't providing maximum grip...
On a FWD car the rear only has to follow the front...like a pair of castors really...so it's accepted practice to get the front gripping and then set the rear pressures higher...
Try the fronts at the setting for 2 people and no luggage (or even slightly less to aid grip, feel etc)...and the rears at the setting for 4 people and a boot full of luggage (or even slightly more)
That should be a good starting point...
On the road, I don't like the rears being too high on a FWD car, otherwise it gets unstable and it likely to swap ends if you lift off mid bend...but I do like it to be at the point of breaking away with little provocation to enable the rear to rotate.
Lift off oversteer is great if you have lots of grip at the front (aggressive suspension angles, sticky tyres and an LSD - which I do) but no use if you can't power out of the slide you have put the car in....so be careful how high you go on rear pressures.
I can't remember what I run my Golf at...something like 30F/35R or 32F/36R, somewhere around there. That's on 215/40/16s on 7" x 16" BBS wheels.
I'd know if I saw what the Mk3s run standard...but that's in the right ballpark.
Play about though...