I don't even want to ask this question but... several years ago we hired a local contractor to spray high density foam on the roof deck and walls of our unfinished 2nd floor. We realized that the job was done poorly and cut an access into the attic space to assess things. We realize now that they spray foamed directly to the chimney (no flashing). The chimney is currently used for a woodstove and DHW venting. The DHW will go away but wood stove will remain. My question is, how bad (unsafe) is this? I have found information on foam exposure to fire but have not been able to find anything about temperature ratings in general (i.e. what happens on prolonged exposure to high temperatures).
Closed-cell spray insulation, a rigid medium-density material, can be used in exterior applications such as continuous insulation applications, as well as interior applications. This type of foam insulation has a higher R-value per inch making it also suitable for small areas that require the highest possible R-value to meet building code requirements. Closed-cell spray foam’s rigidity help reject bulk water making it a recognized flood-resistant material by FEMA.
There are several types of reflective roof coatings that impart varied reflectance rates/ values. Typically, the reflective coatings are what are commonly referred to as white coatings and there are also aluminum coatings typically used with asphalt. Highly reflective white roof coatings are typically comprised of acrylics, urethanes, silicones, SBS, SEBS, and other types. https://youtube.com/v/ggLAUsiuI_o?version=3
As this example illustrates, it's important to seal the envelope completely. One of spray foam's biggest selling points is its air-sealing ability, but it can't seal places where it's not sprayed. One of the nice things about using spray foam in new construction is that you can do a Blower Door test before the drywall goes in. Even better, you can test for leaks with a fog machine.
Here's a simpler, less expensive alternative: Cut some 2-inch-thick rigid-foam insulation and glue it to the subfloor between the joists or support it with nails driven partway into the joists. Then fill any gaps between the edges of the foam boards and the joists using the canned spray foam sold at home centers or hardware stores. An even easier option is to nail the foam panels against the bottom edge of the joists and seal the joints with canned foam, but you'll lose some headroom and access to any pipes and wires between the joists. As with spray-foam kits, protect yourself and the floor from the dripping globs of canned foam. A full face shield, gloves, and a hat would be a good start.

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As an industry leader in high performance building products, we were the first in the world to commercialize the latest state-of-the-art spray foam insulation technology. Our corporate headquarters in Houston, TX is home to multiple laboratories, customer care, technical services and a world class manufacturing plant that produces spray foam and elastomeric roof coatings. We are constantly striving to raise the bar in energy efficiency and sustainable building practices.

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Spray foam is a fully adhered insulation that is spray applied into wall cavities, providing a continuous air and moisture barrier. Spray foam allows efficient use of your HVAC system and helps regulate the temperature fluctuations and humidity in your home. Spray foam effectively seals the building envelope, filling in any cracks and crevices, the common source of air and moisture infiltration as well as temperature variations.

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I've seen this only once, and it was with closed cell foam, but I've heard of it happening with open cell foam, too. I don't know the details, but I've heard it could result from a bad batch of chemicals, improper mixing, or too high a temperature. Whatever the cause, it's not a good thing. The photo below shows how the spray foam pulled away from the studs. A little bit of uninsulated area like that adds up to a lot of heat loss/gain when the whole house has that problem, as it did here.

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Though foam insulation has a higher upfront cost than fiberglass or cellulose, it recoups this expenditure in a relatively short period of time. Additionally, the insulation’s permanence means that it will continue to generate savings over the life of your structure. The durability of this insulation means that you can rest easy in the knowledge that at least one component of your structure will stand the test of time. https://youtube.com/v/ggLAUsiuI_o
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