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I DC after shampooing. I use Sabino Moisture Blok which is a very heavy silicone serum so I don't think any DC would penetrate properly if I don't shampoo first.
I do hate hopping in and out of the shower though so to solve that I just use DCs that are meant to work in 10 minutes or less. I'm currently using the It's a 10 DC and it says to leave on for 2-5 minutes so I just keep it in while I clean my body. That is enough time for it to work and condition my hair nicely.
I like to DC after. I cowash or shampoo in the shower, apply my DC and cover with a plastic cap. I keep and plastic cap and scarf on after my shower for about 30-60 minutes (sometimes I also sit under my hooded dryer). I rinse it out over my tub with the shower running so that I don't have to jump back in the shower.