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).
You've got no argument from me there, Dennis. Getting a good installer if you're going with spray foam is crucial. Many builders or homeowners don't know how to find one, however, and that's where third party inspections come in. Also, even good installers have bad days, but if someone comes in behind them with a measuring probe and a Blower Door, there will be fewer sub-par foam jobs.  
Although spray foam insulation has been in use since the 1940s, primarily for aircraft, for the past 30 years, continual product innovation has seen the increased adoption of spray foam insulation in residential and commercial construction. The rapid growth of sprayed foam insulation in building construction, thanks in part to its immediate and long-term benefits, has allowed the insulation material to sit confidently alongside traditional insulation types in providing thermal comfort for building occupants. https://youtube.com/e/ggLAUsiuI_o?app=desktop

Closed-cell (aka two-pound foam) is denser than open-cell at about 2 pounds per cubic foot. Its R-Value is between 6-6.5 per inch. As a result, this kind of foam is much more expensive than its counterpart. The reason closed-cell doesn't need a vapor retarder is because it already has one. It's permeance is 0.8 perm, which means it can handle cold climates without the use of an additional board or drywall. Closed-cell uses hydroflurocarbons (HFCs) as part of its makeup. However, this material has been known to have a high global warming effect. If you want a green insulation solution, this is not the material to use. A way to avoid this and still use closed-cell is by installing it alongside fiberglass batts.
This high R-value of 4.45 at 1 inch, polyurethane insulation expands to seal cracks, gaps, and voids in attics, walls, crawl spaces, and ceilings. Agribalance is a three-quarter pound density foam that reduces air leakage by improving energy efficiency, and reducing moisture intrusion and outside contaminants such as dust, dirt, and allergens. As a result, builders can generally install smaller, more energy-efficient HVAC systems and achieve similar, or superior comfort compared to traditionally insulated structures which require a larger, less efficient HVAC system – resulting in higher energy costs.

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