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SuperF4 kills the foreground program when you press Ctrl+Alt+F4. This is different from when you press Alt+F4. Alt+F4 only asks the foreground program to exit, allowing it to decide for itself what to do. .
You can also kill a process by pressing Win+F4 and then clicking the window with your mouse. You can press escape or the right mouse button to exit this mode without killing a program.
SuperF4 should be able to kill all kinds of processes, whether they are hung or not. Beware though, killing a program does not give it a chance to save unsaved work. If you accidentally kill explorer.exe, you can start it again by opening Task Manager (Ctrl+Shift+Esc).