the shim sits loose between the cpu surround and the heatsink for socket cpus. It is not designed to cool anything, it should not touch the heatsink when it is installed properly.
Putting compound all over your shim will just make a mess - it isn't going to cool anything. Putting anything too much around your shim may cause it to push up on the heatsink, preventing the heatsink sitting properly on the cpu die and that is a really bad thing.
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