Overpressurising is caused by air getting into the system.
As you know the coolant system is pressurised under normal operation.
However if there is a small leak in the system, then the following can happen...
A small leak can allow water to be pushed out under pressure...eg engine under load.
However, when that pressure is reduced, ie. when the load is reduced then a vacuum is formed at the leak.
This then sucks in air...
When air is heated it expands and takes up more "space" than water.
Get enough air in the system (and it doesn't require much) and the system becomes overpressurised causing overheating problems.
Dead giveaways are rock hard coolant pipes pipes and a "hissing" from the coolant cap as it tries to vent off the excess pressure.
If you suspect this, BE VERY CAREFUL when loosening the cap as the water will be above boiling point and under tremendous pressure.
Use a towel and VERY gently turn the cap so it just starts to release pressure. Turn it too quickly and the cap will blow straight off and soak you in boiling water!!
This has happened to me and it is very very unpleasant!
Now move away and leave it for a few minutes to allow the pressure to vent off safely.
The most common cause of air getting into the system is a a split in the heater bypass valve. As many of you know, that is situated at the back of the engine, towards the drivers side.
Don't try and drive the car unitl the problem is resolved. The pressure and heat can cause failure of other components very quickly.