# MEMORANDUM
To: Margaret Sheppard, U.S. EPA Cc: Bella Maranion , Melissa Fiffer, and Rebecca von dem Hagen, U.S. EPA From: Molly Griffin, Christine Wrublesky, Rebecca Ferenchiak, Jenny Tanphanich, and Mark Wagner, ICF International Date: May 7, 2013 Re: Solvay Solkane HFC
- 365mfc and HFC
- 227ea Blend (EPA Contract Number EP
- W
- 10
- 031 Task Order 205 , Task 04)
This risk screen does not contain Clean Air Act (CAA) Confidential Business Information (CBI) and, therefore, may be disclosed to the public. The purpose of this memorandum is to supplement EPA’s Background Document on the foam blowing agent sector (EPA 1994) and assess the risk associated with use of blends of HFC
- 227ea and HFC
- 365mfc in this sector
. To assess the flammability and consumer exposure risks associated with use of Solkane® 365/227, Solvay Fluoride s ’ trade name for blends of HFC
- 365mfc and HFC
- 227ea, ICF has reviewed the new information available regarding this blend , in addition to the data submitted for each component of the blend in previous SNAP submissions . EPA previously reviewed and found HFC
- 3 65mfc to be acceptable for most end
- uses within the foam blowing agent sector (EPA 2010a) . EPA also has listed HFC
- 227ea as acceptable for use in the aerosols and fire suppression sectors (EPA 2010b) but has not reviewed HFC
227ea in the past for use in fo am blowing
. The remainder of this memorandum is organized into the following sections:
• Section 1: Flammability; • Section 2: Consumer Exposure to Decomposition Products; • Section 3: Discussion; and • Section 4: References. Please contact Mark Wagner at 202
- 862
- 1155 with any questions or comments.***** FINAL May 7, 2013 ***** 1 

## 1. Flammability EPA’s Significant New Alternatives Policy (SNAP) Program has concerns about the risks of using flammable foam blowing agents
. HFC
- 365mfc is flammable when its concentration in air is in the range of 3.8 percent to 13.3 percent by volume ( i.e., equal to between 38,000 ppm and 133,000 ppm). In certain end
- uses , and particularly in spra y foam applications , foam blowing agents may be exposed to a potential source of ignition during their application. For example, use of spray foam in roofing applications may expose the blowing agent to tar . Commonly used in the construction of roofs, tar has a flashpoint of ≥ 450°F and is applied at temperatures ranging from 330°F to 440°F , presenting a risk of ignition
. Hence, to mitigate the risk of overheating or ignition , it is important to carefully mo nitor the temperature of the foam blowing agent and other products (e.g., tar) or equipment used in close proximity to the blowing agent
. Solvay Fluorides’ approach to addressing the potential flammability risk for foams is to formulate blends of HFC
- 365mfc with non flammable compounds , yielding non flammable blends. This is a well
- known technique, and is commonly applied. HFC
- 227ea, which Solvay is proposing to be blended with HFC
- 365mfc, is classified as nonflammable by ASHRAE
. According to flammability testing data provided by the submitter, blends of HFC
227ea and HFC
- 365mfc are nonflammable as long as HFC
- 227ea makes up at least 4% of the foam blowing agent mixture (Solvay 2009). Solkane® 365/227 will consist of either 93% HF C
- 365mfc and 7% HFC
- 227ea , or 87% HFC
- 365mf c and 13% HFC
227ea (by weight) (Solvay 2012a), rendering the blends nonflammable
. However, due to the difference in vapor pressures and boiling points of the two constituents, HFC
- 227ea is expected to evaporate a t a faster rate than HFC
- 365mfc (see Table 1), thereby reducing the concentration of HFC
- 227ea in the remaining blend; as the amount of HFC
- 227ea in the blend decreases, the remaining blend will become increasingly flammable. Table 1 . Chemical Properties of HFC - 365mfc and HFC - 227ea Chemical Property HFC
- 365mfc a HFC
- 227ea b Vapor Pressure at 20*C 43.3 kPa 390 kPA Boiling Point 40.1°C
- 16.5°C a Solvay (2011a) b Solvay (2011b) Evaporation of HFC
- 227ea may occur during storage of the blend in a tank and during storage and use of the blend in its application container
. However, b ased on the thermodynamic properties of the two constituents, significant differential evaporation of HFC
- 227ea to the headspace is not e xpected to occur during proper storage of these containers (i.e., properly closed and protected from physical damage ) (Solvay 2005). Solkane® 365/227 will be produced in blends with concentrations of HFC

- 227ea that are significantly higher than the 4% needed to render the blend nonflammable
. Nevertheless, to minimize any risk during storage of the blend, ICF recommends that Solkane® 365/227 be stored in containers that are kept closed and located in a cool, well
ventilated location away from heat and so urces of ignition, in accordance with the proposed substitute’s MSDS. Spills of Solkane® 365/227 should be cleaned by first covering the spill in order to slow down the evaporation of HFC
- 227ea, and then soaked with an inert absorbent material. To minimize any risk during use of the blend, any containers of Solkane® 365/227 should be tightly closed (sealed) when not in use. ICF further recommends that only personnel trained specifically for dealing with flammability hazards use Solkane® 365/227 and that ot her safety precautions outlined in the proposed substitute’s MSDS and by the foam blowing industry be followed. When the proposed substitute’s MSDS and additional safety precautions outlined above are followed, ICF does not believe that evaporation of HFC
- 227ea***** DRAFT ( May 7, 2013 )

- DO NOT QUOTE OR CITE ***** 2 would be significant enough to lead to an over
- concentration of HFC
- 365mfc in the blend, and hence would not present a significant flammability risk. 

## 2. Consumer Exposure to Decomposition Products After their application, it is possible that blowing agents will decompose and form toxic decomposition products over time within the cells of closed cell rigid foams . G radually, these substances may migrate from the foam matrix and leach into the air . This is a particular concern in foam blowing end uses for foams that are used in locations where persons are regularly present for extended periods, such as in a home or apartment
. To assess the risk of exposure to consumers, EPA evaluates whether any decomposition products may be carci nogenic and whether the concentration of decomposition products is sufficiently high to be of concern. The level of concern for decomposition products established in the Background Document was 2,000 ppm (by weight, relative to the blowing agent). Risks below this level are considered acceptable in the context of EPA’s decision making. To evaluate the risk of consumer exposure to the decomposition products of Solkane® 365/227, ICF reviewed the information provided by Solvay regarding the potential decomposition of HFC
- 365mfc, and blowing agent blends containing HFC
- 365mfc and HFC
- 227ea, as summarized below. Information regarding the decomposition of HFC
- 365mfc was provided in a previous submission by the company , but only minimal information was av ailable for HFC
- 227ea and the proposed blend
. HFC - 365mfc Since the original SNAP approval of pure Solkane ® 365mfc, the submitter has performed additional testing and found Solkane ® 365mfc to be stable up to approximately 200 °C (392°F)
. In the presence of fire (i.e., temperatures at or above 200 ° C [392°F] ) , HFC
- 365mfc may decompose to form hydrogen fluoride , fluorophosgene, and potentially other hazardous decomposition products that are reasonably anticipated to be produced by the breakdown of most foams i n the presence of fire (Solvay 2012b ) . During accelerated aging tests of certain formulations containing HFC
- 365mfc at 70 ° C (158 ° F) , it was observed that cis
- and trans
1,1,1,3
- tetrafluorobut
- 2
- ene and 1,1,3,3
- tetrafluorobut
- 1
- ene were formed
. H owever, these temperatures are not expected to be reached during typical residential use of foams and thus, it is unlikely that the identified breakdown products will be generated or that consumers would be exposed (Solvay 2009)
. Solvay has also tested the degradation of HFC
- 365mfc as a result of contact with formulated polyols. During this testing, it was observed that C 4 fluorinated olefins are generated and released in the vapor phase layer above the polyol formulation at a maximum concentration for all decomposition products of 0.1% by volume , or 1 , 000 ppm (Solvay 2009) . This is below the level of concern for aggregate initial concentrations of decomposition products ( i.e., 2 , 000 ppm ) established in EPA’s Background Document
. HFC - 227ea HFC
- 227ea was p reviously SNAP
- approved for use in the aerosols and fire suppression sectors (EPA 2010b). Information regarding the use of HFC
- 227ea alone as a foam blowing agent, and its potential degradation products in foam was not readily avai lable . H owever, ICF believes that the information provided on HFC
365mfc (which composes the majority of the blend), and the information provided on the blend (as summarized below) is sufficient to evaluate the risk of consumer exposure to de composition products of the propos ed blend. Sol kane ® 365/227 For both product blends of Solkane® 365/227 , it was shown that there is no temperature influence up to 200 ° C (Solvay 2012a), similar to neat HFC
- 365mfc
. C ell gas analysis showed no products inside the foam with in a detection lim it of approximately 200 ppm (Solvay 2012a) , which is well below EPA’s 2,000 ppm level of***** DRAFT ( May 7, 2013 )

- DO NOT QUOTE OR CITE ***** 3 concern. In addition, according to the submitter, this blend has been used in the industry outside the U.S. for approximately 7 years with no reports of decomposition ( Solvay 2012a ). Given the decomposition products’ relatively low concentrations and lack of indication of unusual toxicity or carcinogenicity, ICF believes there is not a significant toxicity concern and that the consumer risks from decomposition products are acceptably low. 

## 3. Discussion EPA previously found HFC
- 365mfc acceptable in all foam blowing end
- uses except in spray foam and blends of HFC
- 365mfc and HFC
- 245fa containing at least 5% HFC
- 245fa acceptable in spray foam
. Similar to the use of HFC
- 245fa in Solvay’s 365/245 blend, HFC

- 227ea will be blended in small quantities with HFC
- 365mfc in order to reduce the overall blend’s flammability. The use of HFC
- 227ea in this blend is anticipated to minimize any risks of flamma bility to consumers or workers, and use in accordance with the proposed substitute’s MSDS will address risks of flammability due to differential evaporation of HFC
- 227ea from the blend. Given the relatively low concentrations of the decomposition products, the lack of any indication of unusual toxicity or carcinogenicity of the decomposition products, ICF believes that Solkane® 365/227 does not present a significant toxicity concern and that the consumer risks from decomposition products are acceptably low
. 

## 4. References EPA 1994. Significant New Alternatives Policy Technical Background Document: Risk Screen on the Use of Substitutes for Class I Ozone
- depleting Substances: Foam
- Blowing Agents . Stratospheric Protection Division. March, 1994. EPA 2010 a . “Foa m Sector Substitutes under SNAP as of June 16, 2010.” Available online at: http://www.epa.gov/ozone/snap/foams/foams.pdf
. EPA 2010 b . “ List of Substitutes .” Last updated on August 19, 2010. Available online at: http://www.epa.gov/ozone/snap/lists/index.html
. Scientific & Regulatory Solutions. 2009. Re: Supplemental Information
– Solkane® 365mfc SNAP Submission. Submitted on beha lf of Solvay Fluorides, LLC. June 2009. Solvay Fluorides 2005. “Flammability Characteristics and Handling for Solvay 365mfc and Solvay 365mfc/227.” Available online at http://www.solvaychemicals.com/Chemicals%20Literature%20Documents/Fluor/HFC/Tech_Solkane_365mfc_ and_365_227_Handling_EN.pdf . Accessed April 27, 2012. Solvay Fluorides 2008. Significant New Alternatives Pol icy Program Submission to the United States Environmental Protection Agency, October 2008. Solvay Fluorides 2009. TSCA/SNAP Addendum Submission to the United States Environmental Protection Agency for Solkane 365®. Received November 25, 2009 . Solvay Fluo rides 2010a. “Safety Data Sheet for Solkane® 365/227 87/13.” North American Version. March 24, 2010. Available online at http://www.solvaychemicals.us/SiteCollectionDocuments/sds/P19464

- USA.pdf
. Accessed April 27, 2012. Solvay Fluorides 2010b. “Safety Data Sheet for Solkane® 365/227 93/7.” North American Version. March 24, 2010. Available online at http://www.solvaychemical s.us/SiteCollectionDocuments/sds/P19465

- USA_CN_EN.pdf . Accessed April 27, 2012.***** DRAFT ( May 7, 2013 )

- DO NOT QUOTE OR CITE ***** 4 Solvay Fluorides 2011a. “Safety Data Sheet for Solkane® 365.” North American Version. August 31, 2011. Available online at http://www.solvaychemicals.us/SiteCollectionDocuments/sds/P19504

- USA.pdf . Accessed April 27, 2012. Solvay Fluorides 2011b. “Safety Data Sheet for Solkane® 227.” North American Version. October 10, 2011. Available online at http://www.solvaychemicals.us/Si teCollectionDocuments/sds/P19476

- USA.pdf . Accessed April 27, 2012. Solvay Fluorides 2012 a . Re: Supplemental Information
- SNAP Submission for Solkane® 365/227. January 30 , 20 12 . Solvay Fluorides 2012 b
. Response to A Few More Questions on SNAP Submission fo r Solkane® 365/227. March 29 , 2012.