Adhesion seems better at higher temperatures. Consider an option to specify a different temperature for the first layer.
I always set the cura temp to 0 and set the temp with the ulticontroller (or cura). I usually make the first layer hotter at 240C and then when almost done with first layer I lower the temp. No need for this to be done automatically.
Having the temp set to 0 is nice cause I can start the print as the temp is passing 235 and by the time the home is finished and the brim or skirt are started the temp is close enough to 240 to start.
You can get steeper angles (more than 80 degrees possibly) with thinner layers. You can't make the nozzle hole any bigger (it's .4mm) but the thinner the layers, the less z changes for a sideways movement of up to .4. So if layer height is .1 you should be able to get a slope of 1/4 or arctan(1/4) = 76 degrees from vertical. layer height of .05 in theory gives you atan(1/8) which is 83 degrees from vertical.
Also it's important to keep the part cool (more than 5 seconds per layer and fan on) if you want good overhang results.
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illuminarti 18
You may want to adjust your start gcode to extrude a little more plastic in the home position to avoid the problem with it taking a while to prime the head. I changed the default 3mm extrusion to 6mm to help with this. (I also recommend reducing the speed on that line to F60, to ensure you don't overload the head).
The skirt setting is also intended to provide this extra preliminary extrusion. You don't get that if you have the brim enabled, but then the exact quality of the first layers of brim is less important anyway.
Other slicers do allow for different first layer temperatures. Some people swear by it, but personally I don't see the need. I just print on blue tape, rubbed down with alcohol, and get extremely good adhesion at pretty much all temperatures.
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