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Different erosional features can lead to layers of rock flaking off.

In layered sedimentary rocks this is usually the case when some of the layers are less resistant against weathering (e.g. when the grains are cemented by carbonate which is dissolved by acid rain). One can often see that phenomenon on old sandstone buildings.

Also igneous rocks show the effect of layers flaking off the surface. This may be related to thermal expansion and contraction working mostly on the outer part of large boulders. It might as well have something to do with the structure of the rock inherited from its crystallization and residual stresses and the depth that water can penetrate and weather the rock.

Another answer:

The flaking off in layers of rocks is called exfoliation. This usually occurs in deserts and is caused by changes in temperature.

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Q: What Causes rock to flake off in layers?
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