SPF insulation applied by professionals is usually described as either a high- or low-pressure foam and is available as either open- or closed-cell. Each type has advantages and disadvantages depending on the application requirements. The comparison chart below can be helpful in explaining or understanding which type of SPF insulation is best suited to a specific application. http://www.youtube.com/watch?v=ggLAUsiuI_o&feature=youtube_gdata
In the early days of insulating attics, people believed the insulation was a heat source. That’s not the case, as the insulation is actually a barrier between two areas of different temperatures. As for the “hot roof” theory, the unvented attic system could make the temperature of the roof go up a little, but this increase won’t cause damage to your shingles. https://youtube.com/v/ggLAUsiuI_o?version=3
While coatings may potentially stop minor leaks, the roof should be properly repaired and dried prior to coating application. Coatings may be able to seal pinhole leaks, which are leaks not visible to the naked eye. If the roof is leaking, the roof leak will need to be identified and repaired prior to any recoating; do not expect the coating to find and seal the leaks.
Medium-density foam is applied as low or high-pressure two-component polyurethane spray foam. Medium-density foam offers specific benefits depending on the climate and the type of building in which it is used. Like low-density foam, medium-density SPF is often used for continuous insulation, interior wall cavity fill, and unvented attic applications. However, medium-density is a closed-cell spray foam; it is often used where there is need for the greatest R-value insulation per inch possible. Medium-density foam acts as an air, vapor, and water barrier, and can even help reduce noise.
The average price to cover 200 square feet with a foam insulation kit will run between $300 and $600 (about two to three kits). Inside these kits is something called Icynene, a foam made from two liquids that are heated and pushed through a gun on the can. When Icynene is released, it expands up to 100 times its size as it hits the surface area you're covering. These can contain a lot of gasses, making its installation a dangerous process. Even low-pressure sprayers can be harmful to homeowners' health.
These coatings contain various types of acrylic polymer, and are typically formulated to help extend the coating’s life and improve durability. Acrylic coatings are available in a number of colors but are most commonly used as white reflective coatings. Thanks to its durability and low cost, many contractors and facility managers believe this to be the best roof coating.
Although spray polyurethane foam has many advantages over other types of insulation, spray foam installation isn’t foolproof. Some builders have reported problems with sloppy foam insulation. For example, some installers have been known to begin spraying before the chemical components are up to temperature, which can affect component mixing and foam performance. When components are poorly mixed, or mixed in the wrong ratio or at the wrong temperature, cured foam has been known to shrink away from rafters or studs, leaving cracks. Some installers rush through their spraying, resulting in voids.
For maximum durability and leak resistance, we recommend that two coats of topcoat be applied at 100 sq. ft. per gallon, or a minimum of 20 mils dry coating. If two complete topcoats are not applied, always apply two thick coats to problem areas such as scuppers, drain areas, ponding areas, seams, and repaired areas. Avoid using Elastek Solar Magic™ or The Shield™ on ponding roofs. Clean skin and tools promptly with water.
Jennifer, I'm not an expert on the health effects of closed cell foam. A lot of people live in houses with closed cell foam and have no health problems from it, at least not short-term, acute problems. I do know of one person who had it removed from her crawl space because she was convinced it caused her dog to get sick, but I know only what she told me.  
I have to insulate my walls at the end of this week. That does not give me time to procure slow-rise foam, so my stud cavities will be filled with foam before I'm ready to fill the corner voids. I will not be able to drill straight through the corner studs. Instead, I will have to remove material where the studs meet. What sort of tool do you envisioning me holding while I create space to pump foam into my 1972 corner voids?
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).

Steve: If your spray foam installer leaves the vents open, he will be committing the 2nd of the 4 problems I described above. You will most likely have comfort and efficiency problems. You may well have condensation problems. You will be spending a lot of money on a product that likely won't perform as it should. Don't let him leave the vents open. If the installer you've chosen doesn't understand this, you may want to choose someone else. 
R-value is the term given to thermal resistance to heat flow. The higher the R-value of an insulation product, the more effective the insulation properties. Spray polyurethane foam comes in a range of densities and cel structure. Low density foams are referred to as Open Cel SPF while higher density foams are referred to as Closed Cel foam. 1.8-2 pound polyurethane foam has the highest R-value of readily available spray foam insulation used in homes and buildings.[4]

Roof Spray Foam Insulation

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