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"Git Gud, scrub"
"Don't be a noob"
"I can't move out of my mother's basement, so I'm rude on internet forums answering legitimate questions"
Sadly, it is as it is by design. No manual triggers for the demon mode; guess it is an attempt at using some form of strategy, which is slightly interesting. Sorry, pal. Just time it the best you can.
At least the super mode is triggered by something I have at least some rough control over, rather than some kind of "kills over the last 30 seconds" timer like when Serious Sam tried out it's version of a super mode.
go into C:\Users\your pc name\Documents\my games\Painkiller Hell and Damnation\PKHDGame\Config\PKHDGame and search for PKHDGame.PKGame
you can also edit the weapons after your liking inside PKHDWeapon (use some time to understand this else you can end up only boosting enemies ;)
you can read these files with notepad++ or any other text editor, else just google notepad++ or use this link http://notepad-plus-plus.org/news/notepad-6.7.3-release.html (newest version)
edit: in case you did not make a backup of these files and cannot remember the default values then you can delete them and inside steam right click on game select properties & local files click on verify integrity of game cache (never cancel this process) then the files will be restored back to normal again.