There is NO "overflow" pipe on an unvented cylinder!!! There is a D1 pipe which carries water from the cylinder to the tundish and there is a D2 pipe which discharges water from the tundish to an appropriate dispersal point!
Problem could be a faulty Temperature relief valve or a faulty Expansion valve or a faulty Expansion vessel
Dont mess about with this, get a qualified plumber who holds a G3 qualification to have a look at it!
Ram It, March 2011