Any idea of what was on the board, where the char is?
I agree that the PCB itself doesn't appear to have been much of a fuel source. I believe FR-4 is more glass, than resin, so shouldn't burn much any way. Yes, the plastic insulator card and possibly some of the components were probably the major fuel sources. What tends to happen is, heat due to excessive power consumption, causes pyrolysis of organic matter (plastics, rubbers, paper etc), releasing various toxic, flammable and explosive gasses: carbon monoxide, hydrogen, benzene and tars. If there's no source of ignition, you'll smell and see some of these gasses as a nasty agic smoke, if there's an ignition source, such as a spark or it reaches the autoignition temperature, the result will be a flame. An explosion can occur, when flammables gasses mix with air before ignition from spark or it reaching its autoignition temperature.
Flame retardants can help prevent fire, but they won't stop it completely and if there's enough heat, from another source, such as a nearby fire, an arc or just Ohmic heating, they can be rendered ineffective.