Problem is going to be fittings.
If you have an ALU rad, you could mill a waterblock base out of ALU, after all nobody says the WHOLE block needs to one material. Most current blocks are not CU either, they are plexi or delrin or the like; just the cool/base plate is copper.
So, you could mill a WB out of ALU. Although it will need to be thicker, just as with the (rolled) steel cases, milled ALU lacks a certain "strength" , so the baseplate would need to be thicker to avoid excessive flex. And since its thermal properties are already less as copper, you'll loose performance twice.
Not to say it can't be done.. it was done in the past (eg Zalman).
But, the main problem is fittings... either go all plastic fittings, or stainless steel, because for ALU fittings.. i wouldn't even know where to look for them.
Now, if you want *real* performance edge... Sterling Silver is an option
Although it might require a custom build radiator.