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Yep. You want to focus on the major points of heat transfer resistance, like the radiator, if you want to improve performance. Heat moves very efficiently across a piece of copper. There's no gain in improving that.
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Don't be silly. You can line an unlimited number of radiators until you run out of space. If you have the will its not hard to bring the coolant to within a fraction of ambient. People have done it. Furthermore even a simple heatercore with a modest 120mm fan will cool the water air interface to a lower delta T then the block-water interface.
Now try and get a copper block within 5C of coolant. You can't without TECs (or an innaccurate probe).