It will spontaneously ignite if heated hot enough in the presence of enough air... flame can definitely light it.
Started a stovepipe fire last week... angle grinder on a screw I couldn't back out as it was stripped... grinding away... sniff, sniff... had my hand stabilizing the pipe against the grinder... hmmm, hand's getting kind of warm, HOT!
Stopped grinding and heard the snapping and popping, and just went around and shut off the air. It went out...
Sense will tell you that the larger percentage of chimney fires likely begin in the stovepipe.. or closer to the wood burner than the top of the chimney. Lots of paper and kindling, trying to heat the stove up quick... fire extends into the stovepipe, hits creosote accumulation and it lights, spreads into the chimney...
I reverse engineered a "T" today so it would orient the way I want it to. The male and female parts were in the wrong place. Nowhere near as complicated as a sex change procedure.
Drill out two rivets, remove the piece. Drill out two more, remove that piece. Rivet them back into place when you swap them... oh, pop rivets won't fit outside in in the female part... go from inside out. Use stainless rivets...
Now I have five inches of pipe coming off the "thimble", a "T" with a male down to go into another "T" which I cut a 7 inch BDD into, into another "T", with about five inches of straight pipe into the boiler. Remove the plugs, run a six inch brush in and out, vacuum or sweep the mess out, and put the plugs back. A hand wire brush cleans the "T" with the BDD in it from the top and bottom. Used radiused "T"s so flow would be closer to that of elbows...
Want to keep the chimney connector clean in this situation... I suspect with the BDD, the chain of events leading to a chimney fire will begin with a connector fire. Mixed with the air from the BDD, I don't believe the exhaust would be hot enough to light a chimney fire.
Peak temperatures between the boiler and BDD are 425/450 degrees, above runs around 250/275... while the door on the boiler is 500 degrees.