did I/am I about to have a chimney fire?

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Well, the wood was split in November, but today I split the largest piece I could find and took the reading from that one. So it was a fresh split of a pre-split...

The outside readings are all but meaningless, the inside of a freshly split piece at 20-24% will work, but it's not ideal.

To complicate things further, was this measurement taken on a cold piece of wood from outside? Or on wood that has had a chance to come up to room temp?

I brought a trailer load of wood home yesterday and parked it in the basement garage. Last night, I checked too pieces (this wood is NOT seasoned) and they registered 23-25%. 24 hours later, after the wood has come up to about 60 degrees, I measured the wood and one piece came in at 38%.

Point is, there are a lot of variables. But wood split in November is rarely ready to burn now. For it to be, it would have to be a perfect situation of a dead standing tree. Even then, many dead standing are higher moisture content than many folks care to believe. Good fuel for a wood stove takes time to season once cut, split and stacked.
 
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There is no question that every set up is different and you should always check, inspect your setup regularly throughout the burning season, especially until you know it well enough to know when there is a potential problem. But the pics you have posted don't seem alarming to me. Of course, I am looking at only one part of the set up. My chimney caps always look like that. And my chimneys are clean. I typically clean them once a year just before the burning season starts. That said, that is after years of experience with my setups. In the beginning, I checked, cleaned and checked all burning season. Now, I know my systems and don't worry as much. I know the indicators and just watch for them.
 
Frozen or excessively cold wood will give false readings as noted in another post. I brought some 3 year old hickory in yesterday, Checking them this morning, smaller pieces say about 5-6" are fine but the 9-12" stuff is still at 30% in the middle. not stacked in the best of areas. Large stuff has been split smaller and cross stacked and set aside for next season. I have experienced this before on hickory as well as oak , in this particular location. The dynamics of this particular area have now changed drastically due to some new construction that will be taking place on the adjacent area ( going to be turned into a parking lot) so that will improve things considerably. ( formerly quite shady most of the day due to very large old willows blocking the afternoon sun and of course acting as windbreaks).
 
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