Martin,
I've just dug out my "Metallurgy for Engineers" by Rollason. He has some words on rate of cooling which, if too quick, produces cementite, or white iron. This can be a problem with castings having considerable variation in section – the thin bits cool much quicker than the thicker bits giving a tendency for cementite to form. As one of the other respondents has observed, cementite is very hard and only carbide tipped tools have any chance of cutting through it.
In the old days, iron castings were left in the yard "to weather" before they were machined. This, I believe, allowed the hard surface layer to rust away giving hardened carbon steel or , later, high speed steel half a chance of getting under the "skin" and into the grey iron.
If you can get a copy of Rollason from the library, look up the blackheart process on page271. This gives the correct times and temperatures to develop a machinable structure from a white iron.
Jack Meatcher