ORNL/M-XXXX
and Ceramics Division

REFRIGERATOR INDUSTRY EFFORTS TO REPLACE HCFC-141b AS A BLOWING AGENT FOR URETHANE FOAM INSULATION

K. E. Wilkes and D. W. Yarbrough

Date Published

- September 1996

Prepared for the U. S. Department of Energy Office of Buildings Energy Research

Prepared by OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee 37831 Managed by LOCKHEED MARTIN ENERGY RESEARCH CORP. for the U.S. DEPARTMENT OF ENERGY under contract DE-AC05-96OR22464 

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ORNL/M-XXXX

Metals and Ceramics Division

REFRIGERATORINDUSTRY EFFORTS TOREPLACE HCFC-141b

AS A BLOWINGAGENT FORURETHANE FOAMINSULATION

K. E. Wilkes and D. W. Yarbrough

Date Published

- September 1996

Prepared for the U. S. Department ofEnergy Office ofBuildings Energy Research

Prepared by OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee 37831 Managed by LOCKHEED MARTIN ENERGY RESEARCH CORP. for the U.S. DEPARTMENT OF ENERGY under contract DE-ACOS-960R22464 

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ORNL/M-XXXX

Metals and Ceramics Division

REFRIGERATORINDUSTRY EFFORTS TOREPLACE HCFC-141b

AS A BLOWINGAGENT FORURETHANE FOAMINSULATION

K. E. Wilkes and D. W. Yarbrough

Date Published

- September 1996

Prepared for the U. S. Department ofEnergy Office ofBuildings Energy Research

Prepared by OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee 37831 Managed by LOCKHEED MARTIN ENERGY RESEARCH CORP. for the U.S. DEPARTMENT OF ENERGY under contract DE-ACOS-960R22464E, T
REFRIGERATOR INDUSTRY EFFORTS TO REPLACE HCFC-141b AS A BLOWING AGENT FOR URETHANE FOAM INSULATION

K. E. Wilkes and D. W. Yarbrough

INTRODUCTION The primary insulation used in refrigerators is polyurethane foam. Until recently, these insulations were foamed using CFC-11 (trichlorofluorocarbon). Because of the Montreal Protocol, production of CFC-11 for use as an insulation blowing agent ceased on January 1, 1996. During 1994 and 1995, the refrigerator industry discontinued use of CFC-11 as a blowing agent, and switched primarily to HCFC-141b, with some use of HCFC-142b and HCFC-22. Production and import of HCFC-141b for use as a foam blowing agent is due to cease on January 1, 2003. Because of this, the refrigerator industry is actively searching for a zero-ozone-depletion-potential blowing agent to replace HCFC-141b. This report provides a brief assessment of efforts by the refrigerator industry to, develop replacements for HCFC-141b. Information for this report was obtained primarily from the proceedings of conferences in which the authors participated. These included Polyurethanes 1995, the International CFC and Halon Alternatives Conference, and the International Appliance Technical Conference. Information was also obtained from personalcontacts at meetings of the Insulation Technical Advisory Committee of the Appliance IndustryGovernment CFC Replacement Consortium, Inc. (also known as the Appliance Research Consortium, or ARC). The industries represented in the ARC are listed in Table 1. Other participants are the Department of Energy, the Environmental Protection Agency, and the Electric Power Research Institute. ALTERNATIVE BLOWING AGENTS A systematic search to identify third-generation blowing agents has been performed by the Syracuse Research Corporation and the Environmental Protection Agency. (1) A number of literature sources were searched and a list of about 1000 chemicals was compiled. No chemicals containing chlorine or bromine were included in this master list. They screened this list to 125 chemicals by requiring that the boiling point be between -60°C and 60°C. This range was selected because known or experimental blowing agents for polyurethane foam have boiling points between -50°C (difluoromethane) and 50°C (cyclopentane). Several compounds were eliminated because of factors such as expected reactivity with feedstocks used in polyurethane production, or the inability to estimate the vapor thermal conductivity or boiling point. The final list consisted of 105 chemicals. The 105 chemicals were ranked based on four criteria: • Boiling point. Chemicals with boiling points closest to that of CFC-11 were given the highest ranks. This was based on the presumption that a boiling point as close as possible to that of CFC-11 would result in the least amount of retrofitting of the production processes. 

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REFRIGERATORINDUSTRYEFFORTS TO REPLACE HCFC-141b

AS A BLOWINGAGENTFORURETHANEFOAMJNSULATION K. E. Wilkes and D. W. Yarbrough

INTRODUCTION The primary insulation used in refrigerators is polyurethane foam. Until recently, these insulations were foamed using CFC-I1 (trichlorofluorocarbon). Because oftheMontreal Protocol, production ofCFC-II for use as an insulationblowing agent ceased onJanuary 1, 1996. During 1994 and 1995, the refrigerator industry discontinued use ofCFC-II as a blowing agent, and switched primarily to HCFC-141b, with some use ofHCFC-I42b and HCFC-22. Production and import ofHCFC-141b for use as a foam blowing agent is due to**c~ase** 

### onJanuary 1, 2003. Because ofthis; the refrigerator industry is actively searching for a zero-ozone-depletion-potential blowing agent to replace HCFC-141b. This report provides abriefassessment ofefforts by the refrigerator industry to. develop replacements for HCFC-14Ib. Information for this report was obtained primarily from the proceedings of conferences in which the authors participated. These included Polyurethanes 1995, the International CFC and Halon Alternatives Conference, and the International Appliance Technical Conference. Information was also obtained from personal contacts at meetings ofthe Insulation Technical Advisory Committee ofthe Appliance IndustryGovernment CFC Replacement Consortium, Inc. (also known as the Appliance Research Consortium, or ARC). The industries represented in the ARC are listed in Table 1. Other participants are the Department ofEnergy, the Environmental ProtectionAgency, and theElectric PowerResearch Institute. 

### ALTERNATIVE BLOWINGAGENTS A systematic search to identify third-generation blowing agents has been performed by the Syracuse Research Corporation and theEnvironmental Protection Agency. (1) A number of literature sources were searched and a list ofabout 1000 chemicals was compiled. No chemicals containingchlorine orbromine were included in this masterlist. They screened this list to 125 chemicals by requiring that the boiling point be between -60°C and 60°C. This range was selected because known or experimental blowing agents for polyurethane foam have boiling points between -50°C (difluoromethane) and 50°C (cyclopentane). Several compounds were eliminated because offactors such as expected reactivity with feedstocks used in polyurethane production, or . the inability to estimate the vapor thermal conductivity orboiling point. The final list consisted of 105 chemicals. The 105 chemicals were ranked based on four criteria:

• Boiling point. Chemicals with boiling points closest to that ofCFC-ll were given the highest ranks. This was based on the presumptionthat a boiling point as close as possible to that ofCFC-ll would result in the least amount ofretrofitting ofthe production processes.
1 

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REFRIGERATORINDUSTRYEFFORTS TO REPLACE HCFC-141b

AS A BLOWINGAGENTFORURETHANEFOAMJNSULATION K. E. Wilkes and D. W. Yarbrough

INTRODUCTION The primary insulation used in refrigerators is polyurethane foam. Until recently, these insulations were foamed using CFC-I1 (trichlorofluorocarbon). Because oftheMontreal Protocol, production ofCFC-II for use as an insulationblowing agent ceased onJanuary 1, 1996. During 1994 and 1995, the refrigerator industry discontinued use ofCFC-II as a blowing agent, and switched primarily to HCFC-141b, with some use ofHCFC-I42b and HCFC-22. Production and import ofHCFC-141b for use as a foam blowing agent is due to**c~ase** 

### onJanuary 1, 2003. Because ofthis; the refrigerator industry is actively searching for a zero-ozone-depletion-potential blowing agent to replace HCFC-141b. This report provides abriefassessment ofefforts by the refrigerator industry to. develop replacements for HCFC-14Ib. Information for this report was obtained primarily from the proceedings of conferences in which the authors participated. These included Polyurethanes 1995, the International CFC and Halon Alternatives Conference, and the International Appliance Technical Conference. Information was also obtained from personal contacts at meetings ofthe Insulation Technical Advisory Committee ofthe Appliance IndustryGovernment CFC Replacement Consortium, Inc. (also known as the Appliance Research Consortium, or ARC). The industries represented in the ARC are listed in Table 1. Other participants are the Department ofEnergy, the Environmental ProtectionAgency, and theElectric PowerResearch Institute. 

### ALTERNATIVE BLOWINGAGENTS A systematic search to identify third-generation blowing agents has been performed by the Syracuse Research Corporation and theEnvironmental Protection Agency. (1) A number of literature sources were searched and a list ofabout 1000 chemicals was compiled. No chemicals containingchlorine orbromine were included in this masterlist. They screened this list to 125 chemicals by requiring that the boiling point be between -60°C and 60°C. This range was selected because known or experimental blowing agents for polyurethane foam have boiling points between -50°C (difluoromethane) and 50°C (cyclopentane). Several compounds were eliminated because offactors such as expected reactivity with feedstocks used in polyurethane production, or . the inability to estimate the vapor thermal conductivity orboiling point. The final list consisted of 105 chemicals. The 105 chemicals were ranked based on four criteria:

• Boiling point. Chemicals with boiling points closest to that ofCFC-ll were given the highest ranks. This was based on the presumptionthat a boiling point as close as possible to that ofCFC-ll would result in the least amount ofretrofitting ofthe production processes.
1

# CRAFT

Molecular weight. The lowest molecular weights were given the highest ranks. This was based on the expectation that the lower the molecular weight, the lower the cost per unit weight. • Global warming potential. The chemicals with the highest reaction rates with hydroxyl radicals were given the highest rankings. This is an indicator of the rate of removal of the chemical from the atmosphere. Vapor thermal conductivity. The chemical with the lowest vapor thermal conductivity was given the highest ranking. The vapor thermal conductivity of the blowing agent is an indicator of the energy performance of a foam insulation, with lower thermal conductivities giving lower energy usage. Toxicity was not included in the criteria because of the lack of confidence in available estimation methods. The above four criteria were given equal weighting, and the chemicals were ranked from 1 to 105. The 105 chemicals are listed in Appendix A in order of their overall ranking. Appendix A also gives the ranking for each of the above four criteria. We have correlated the rankings for each of the four criteria against the overall ranking, and found the following correlation coefficients: +0.63 for global warming potential, +0.61 for molecular weight, -0.10 for vapor thermal conductivity, and +0.66 for boiling point. This shows that, while there are reasonably good correlations between the overall ranking and global warming potential, molecular weight, and boiling point rankings, there is very little correlation between the vapor thermal conductivity ranking and the overall ranking. The Appliance Research Consortium has divided candidate replacement blowing agents into three groups.(2) Group A includes those chemicals that are now commercially available and have been used as a blowing agent for refrigerator insulation: cyclopentane, HFC-134a, and carbon dioxide. Group B includes those that are available in sample quantities large enough for tests on refrigerator cabinets. These are HFC-245fa, HFC-236ea, HFC-356mffm, and HFC-365mfc. Group C includes special new chemicals such as fluoroiodocarbons (FICs) that would only be available in sufficient quantities for testing under an expensive program. At present the ARC is not working with any Group C chemicals. They are proceeding with tests on the above chemicals from Groups A and B, as discussed below. Alternative blowing agents presently being investigated in Japan are HFC-152a, HFC-236ea, HFC-245ca, HFC-245fa, andHFC-356mffm.(2) Results of tests with these blowing agents are discussed below. In Europe, the primary blowing agent currently being used for refrigerators is cyclopentane.(3) In addition, there is small amount of use of HFC-134a and HCFC-141b in Europe. Prior to the
2 •



### •

• 

# ORAET

Molecular weight. The lowest molecular weights were given the highest ranks. This was based on the expectation that the lowerthe molecularweight, the lowerthe costperunit weight. Global warming potential. The chemicals withthe highest reaction rates with hydroxyl radicals were given the highest rankings. This is an indicator ofthe rate ofremoval ofthe chemical from the atmosphere. Vaporthermal conductivity. The chemical with the lowest vaporthermal conductivity was given the highest ranking. The vaporthermal-conductivity oftheblowing agent is an indicator ofthe energy performance ofa foam insulation, with lowerthermal conductivities giving lower energyusage. Toxicity was not included in the criteriabecause ofthe lack ofconfidence in available estimation methods.

- The above four criteria were given equal weighting, and the chemicals were ranked from 1to 105. The 105 chemicals are listed in Appendix A in order oftheir overall ranking. Appendix A also gives the ranking for each ofthe above four criteria. We have correlated the rankings for each of the four criteria against the overall ranking, and found the following correlation coefficients: +0.63 for global warming potential, +0.61 for molecularweight, -0.10 for vaporthermal conductivity, and +0.66 for boiling point. This shows that, while there are reasonably good correlations between the overall ranking and global warming potential, molecularweight, and boiling point rankings, there is very little correlation betweenthe vaporthermal conductivity ranking and the overall ranking. The Appliance Research Consortium has divided candidate replacement blowing agents into three groups.(2) Group A includes those chemicals that are now commercially available arid have been used as a blowing agent for refrigerator insulation: cyclopentane, HFC-134a, and carbon dioxide. Group B includes those that are available in sample quantities large enough for tests on refrigerator cabinets. These are HFC-245fa, HFC-236ea, HFC-356mffm, and HFC-365mfc. Group C includes special new chemicals such as fluoroiodocarbons (PICs) that would only be available in sufficient quantities for testing under an expensive program. At present the ARC is not working with any Group C chemicals. They are proceeding with tests on the above chemicals from Groups A and B, as discussed below. Alternative blowing agents presently being investigated in Japan are HFC-152a, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-356mffm.(2) Results oftestswith these blowing agents are discussed below. In Europe, the primary blowing agent currently being used for refrigerators is cyclopentane.(3) In addition, there is small amount ofuse ofHFC-134a and HCFC-141b in Europe. Priorto the


### 2 •



### •

• 

# ORAET

Molecular weight. The lowest molecular weights were given the highest ranks. This was based on the expectation that the lowerthe molecularweight, the lowerthe costperunit weight. Global warming potential. The chemicals withthe highest reaction rates with hydroxyl radicals were given the highest rankings. This is an indicator ofthe rate ofremoval ofthe chemical from the atmosphere. Vaporthermal conductivity. The chemical with the lowest vaporthermal conductivity was given the highest ranking. The vaporthermal-conductivity oftheblowing agent is an indicator ofthe energy performance ofa foam insulation, with lowerthermal conductivities giving lower energyusage. Toxicity was not included in the criteriabecause ofthe lack ofconfidence in available estimation methods.

- The above four criteria were given equal weighting, and the chemicals were ranked from 1to 105. The 105 chemicals are listed in Appendix A in order oftheir overall ranking. Appendix A also gives the ranking for each ofthe above four criteria. We have correlated the rankings for each of the four criteria against the overall ranking, and found the following correlation coefficients: +0.63 for global warming potential, +0.61 for molecularweight, -0.10 for vaporthermal conductivity, and +0.66 for boiling point. This shows that, while there are reasonably good correlations between the overall ranking and global warming potential, molecularweight, and boiling point rankings, there is very little correlation betweenthe vaporthermal conductivity ranking and the overall ranking. The Appliance Research Consortium has divided candidate replacement blowing agents into three groups.(2) Group A includes those chemicals that are now commercially available arid have been used as a blowing agent for refrigerator insulation: cyclopentane, HFC-134a, and carbon dioxide. Group B includes those that are available in sample quantities large enough for tests on refrigerator cabinets. These are HFC-245fa, HFC-236ea, HFC-356mffm, and HFC-365mfc. Group C includes special new chemicals such as fluoroiodocarbons (PICs) that would only be available in sufficient quantities for testing under an expensive program. At present the ARC is not working with any Group C chemicals. They are proceeding with tests on the above chemicals from Groups A and B, as discussed below. Alternative blowing agents presently being investigated in Japan are HFC-152a, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-356mffm.(2) Results oftestswith these blowing agents are discussed below. In Europe, the primary blowing agent currently being used for refrigerators is cyclopentane.(3) In addition, there is small amount ofuse ofHFC-134a and HCFC-141b in Europe. Priorto the


### 2implementation of cyclopentane, carbon dioxide was used as a blowing agent in a limited amount

of production

. While cyclopentane has zero ozone depletion potential , there are other concerns that have hindered its immediate adoption by the U

. S. refrigerator industry

. These include a higher insulation thermal conductivity that results in higher energy usage for refrigerators/freezers, unknown toxicity risk from transfer to food, flammability risks during the foam processing, and an environmental concern about volatile organic compounds

. However, cyclopentane is still being viewed as a possible alternative blowing agent for use in refrigerators and freezers in the U. S.(2) The use of isopentane and normal pentane as less expensive alternatives to cyclopentane has been explored in Europe.(4) Both isopentane and normal pentane have vapor thermal conductivities that are higher than that of cyclopentane and would be expected to produce foams with higher thermal conductivity as well. There is continued interest in carbon dioxide as a blowing agent for polyurethane

. During the foaming of polyurethane, water reacts with isocyanate (one of the batch ingredients) and liberates carbon dioxide. Studies have been performed on improvements to foams blown with carbon dioxide from this water

-isocyanate reaction.(5,6) An alternative which uses liquid carbon dioxide as the blowing agent has been reported.(7) Other blowing agents being explored include HFC-245eb (8,9), perfluorobutyl

-ethylene (10), flourinated ether ( 11), and azeotropes of hydrocarbons with carboxylic acid esters, ketones, or ethers (12). The remainder of this report will focus on those blowing agents under active study by the U. S. and Japanese refrigerator industry as replacements for HCFC-141b

. These are listed in Table 2. Table 2 also shows the correspondence between the names used by the refrigeration industry and the chemical names given in Appendix A. ENERGY EFFICIENCY The ARC has conducted an experimental program to test the energy efficiency of the alternative blowing agents.(2) The blowing agents evaluated in this program were HCFC

- 141b (for a baseline), carbon dioxide, cyclopentane, HFC-134a, HFC-236ea, HFC-245fa, HFC-356mffm, and HFC-365mfc. Refrigerator cabinets and doors were foamed with each ofthese blowing agents and two types of energy tests were run. The first energy test was the DOE test, where the refrigerator is placed in a 90°F environment, with the cabinet operating, the doors closed, and the defrost cycle turned on. When electric anti-sweat heaters were used, the tests were conducted with the heaters on and off and the results were averaged. For the Group B blowing agents, the tests were conducted only with the heaters on, which is a departure from the DOE test. The other type of test was the reverse heat leak test, which is performed on a nonoperating refrigerator

. Here, the unit is placed in a 0°F test chamber, and the'interior of the cabinet is controlled to higher temperatures using
3 

# DRAB
implementation ofcyclopentane, carbon dioxide was used as a blowing agent in a limited amount ofproduction. While cyclopentane has zero ozone depletion potential, there are other concerns that have hindered its immediate adoption bythe U. S. refrigeratorindustry. Theseinclude a higher insulation thermal conductivitythat results in higher energyusage for refrigerators/freezers, unknowntoxicity risk from transfer to food, flammability risks during the foam processing, and an environmental concern about volatile organic compounds. However, cyclopentane is still being viewed as a possible alternative blowing agent foruse 

### in refrigerators and freezers in theU. S.(2) The use ofisopentane and normal pentane as les.s expensive alternatives to cyclopentane hasbeen explored in Europe.( 4) Bothisopentane and normal pentane have vaporthermal conductivities that are higherthanthat ofcyclopentane and would be expected to producefoams with higher thermal conductivity as well. There is continued interest in carbon dioxide as a blowing agent for polyurethane.· Duringthe foaming ofpolyurethane, waterreacts with isocyanate (one ofthe batchingredients) and liberates carbon dioxide. Studies have been performed on improvements to foams blownwith carbon dioxide from this water-isocyanate reaction.(5,6) An alternative whichuses liquid carbon dioxide as the blowing agent has been reported.(7) Other blowing agents being explored include HFC-245eb (8,9), perfluorobutyl-ethylene (10), £lourinated ether (11), and azeotropes ofhydrocarbons with carboxylic acid esters, ketones, or ethers (12). The remainder ofthis report will focus on those blowing agents under active studybythe U. S. and Japanese refrigerator industry as replacements for HCFC-141b. These are listed in Table 2. Table 2 also shows the correspondencebetweenthe names used by the refrigeration industry and the chemical names given in Appendix 

### A. 

### ENERGY EFFICIENCY The ARC has conducted an experimental programto test the energy efficiency ofthe alternative blowing agents.(2) The blowing agents evaluated in this program wereHCFC-141b (for a baseline), carbon dioxide, cyclopentane, HFC-134a, HFC-236ea, HFC-245fa, HFC-356mffm, and HFC-365mfc. Refrigerator cabinets and doors Were foamed with each oftheseblowing agents and two types of energy tests were run. The first energytest was the DOE test, where the refrigeratoris placed in a 90°F environment, with the cabinet operating, the doors closed, and the defrost cycle turned on. When electric anti-sweat heaters were used, the tests were conducted with the heaters on and off and the results were averaged. Forthe Group B blowing agents, the tests were conducted only with the heaters on, which is a departure from the DOE test. The othertype oftestwas the reverse heat leak test, which is performed on a nonoperating refrigerator. Here, the unit is placed in a OaF test chamber, and the"interior ofthe cabinet is controlled to highertemperatures using

3 

# DRAB
implementation ofcyclopentane, carbon dioxide was used as a blowing agent in a limited amount ofproduction. While cyclopentane has zero ozone depletion potential, there are other concerns that have hindered its immediate adoption bythe U. S. refrigeratorindustry. Theseinclude a higher insulation thermal conductivitythat results in higher energyusage for refrigerators/freezers, unknowntoxicity risk from transfer to food, flammability risks during the foam processing, and an environmental concern about volatile organic compounds. However, cyclopentane is still being viewed as a possible alternative blowing agent foruse 

### in refrigerators and freezers in theU. S.(2) The use ofisopentane and normal pentane as les.s expensive alternatives to cyclopentane hasbeen explored in Europe.( 4) Bothisopentane and normal pentane have vaporthermal conductivities that are higherthanthat ofcyclopentane and would be expected to producefoams with higher thermal conductivity as well. There is continued interest in carbon dioxide as a blowing agent for polyurethane.· Duringthe foaming ofpolyurethane, waterreacts with isocyanate (one ofthe batchingredients) and liberates carbon dioxide. Studies have been performed on improvements to foams blownwith carbon dioxide from this water-isocyanate reaction.(5,6) An alternative whichuses liquid carbon dioxide as the blowing agent has been reported.(7) Other blowing agents being explored include HFC-245eb (8,9), perfluorobutyl-ethylene (10), £lourinated ether (11), and azeotropes ofhydrocarbons with carboxylic acid esters, ketones, or ethers (12). The remainder ofthis report will focus on those blowing agents under active studybythe U. S. and Japanese refrigerator industry as replacements for HCFC-141b. These are listed in Table 2. Table 2 also shows the correspondencebetweenthe names used by the refrigeration industry and the chemical names given in Appendix 

### A. 

### ENERGY EFFICIENCY The ARC has conducted an experimental programto test the energy efficiency ofthe alternative blowing agents.(2) The blowing agents evaluated in this program wereHCFC-141b (for a baseline), carbon dioxide, cyclopentane, HFC-134a, HFC-236ea, HFC-245fa, HFC-356mffm, and HFC-365mfc. Refrigerator cabinets and doors Were foamed with each oftheseblowing agents and two types of energy tests were run. The first energytest was the DOE test, where the refrigeratoris placed in a 90°F environment, with the cabinet operating, the doors closed, and the defrost cycle turned on. When electric anti-sweat heaters were used, the tests were conducted with the heaters on and off and the results were averaged. Forthe Group B blowing agents, the tests were conducted only with the heaters on, which is a departure from the DOE test. The othertype oftestwas the reverse heat leak test, which is performed on a nonoperating refrigerator. Here, the unit is placed in a OaF test chamber, and the"interior ofthe cabinet is controlled to highertemperatures using

3

# ORAET

electrical heaters. Finally, thermal conductivity measurements were made on samples of the foam insulation. Average results from the ARC tests are shown in Table 3. Table 4 gives the individual cabinet energy data from which the averages in Table 3 were derived. The results are given as percentage differences between data with the new blowing agent and data with HCFC-141b. A positive value for thermal conductivity, cabinet energy, or reverse heat leak indicates a higher energy usage for the alternative blowing agent than for HCFC- 141b. Table 3 shows that the energy usage with cyclopentane would be about 10 percent higher than with HCFC-141b, and that energy usage with carbon dioxide or HFC- 134a would be more than 10 percent greater than with HCFC-141b. HFC-245fa gave average energy usage and thermal conductivity that were very comparable with HCFC-141b. Individual energy usages for HFC-245fa were both higher and lower than for HCFC-141b. The other three new HFCs (236ea, 356mfc, and 365mffm) had energy usages that were higher than for HCFC-141b, but lower than for cyclopentane. It was noted that the formulations for the four new HFCs have not been optimized, while the commercially available technologies based on cyclopentane , HFC-134a, and carbon dioxide would presumably have been optimized . Even without optimization, the four new HFCs performed better than the three available technologies

. In particular, it was noted that the HFC-365mfc, which had the highest energy usage ofthe four new HFCs, was formulated with a higher than normal amount of water and that it would be expected to perform better ifless water were used in the formulation. While the thermal conductivity of the foam insulation is an indicator of the energy performance of a refrigerator, the percentage change in thermal conductivity due to differences in blowing agent will not generally be the same as the percentage change in energy usage

. This is because of two main factors. The first is that the heat leaks through the insulated walls and doors of a refrigerator/freezer are not the only sources of energy requirements for the entire refrigerator. Other energy requirements arise from heat transfer around door gaskets and at penetrations through the insulation, energy used for anti-sweat heaters, and energy used for the defrost cycle. These other energy sources would tend to make the percentage difference in energy consumption somewhat less than the percentage difference in thermal conductivity. The second factor is related to the temperature imposed on the insulation during a thermal conductivity test as compared with the temperatures experienced by the insulation in an operating refrigerator. In a thermal conductivity test, the mean temperature of the insulation is usually 75°F, while the insulation in a refrigerator is at a lower temperature. The thermal conductivity of foam insulations vary with mean temperature, and different blowing gases give different temperature dependencies

. The result is that the curves of thermal conductivity versus temperature for two blowing agents may get closer together (less percentage difference), farther apart (greater percentage difference), or cross over (reverse in sign of percent difference) as the temperature is lowered from 75°F to the mean temperatures typical of refrigerator operation. Reference 2 also gives results of tests conducted by the Home Appliance Department of the
4 electrical heaters. Finally, thennal conductivity measurements were made on samples ofthe foam insulation. Average results from the ARC tests are shownin Table 3. Table 4 gives the individual cabinet energy data from which the averages in Table 3 were derived. The results are given as percentage differences between data with the newblowing agent and datawith HCFC-141b. A positive value for thennal conductivity, cabinet energy, orreverse heat leakindicates a higher energy usage for the alternative blowing agent than for HCFC-14lb. Table 3 shows that the energy usage with cyclopentane would be about 10 percent higher thanwithHCFC-14lb, and that energy usage with carbon dioxide orHFC-134awould be morethan 10 percent greaterthan with HCFC-141b. HFC-245fa gave average energy usage and thennal conductivitythat were very comparable with HCFC-141b. Individual energy usages for HFC-245fawere both higher and lower than for HCFC-14lb. The other three new HFCs (236ea, 356mfc, and 365rnffm) had energy usages that were higherthan for HCFC-141b, butlowerthan for cyclopentane. Itwas noted that the fonnulations for the four newHFCs have notbeen optimized, while the commercially available technologies based on cyclopentane, HFC-134a, and carbon dioxide would presumably have been optimized. Even without optimization, the four newHFCs perfonned better than the three available technologies. In particular, it was noted that theHFC-365mfc, which had the highest energy usage ofthe four new HFCs, was fonnulated with a higherthan normal amount ofwater and that it would be expected to perform betterifless waterwere used in the formulation. While the thermal conductivity ofthe foam insulation is an indicator ofthe energy perfonnance of a refrigerator, the percentage change in thennal conductivity due to differences in blowing agent will not generally be the same as the percentage change in energy usage. This is because oftwo main factors. The first is that the heat leaks through theinsulated walls and doors ofa refrigerator/freezer are not the only sources ofenergyrequirementsfor the entire refrigerator. Other energy requirements arise from heat transfer around·door gaskets and at penetrations through the insulation, energy used for anti-sweat heaters, and energyused for the defrost cycle. These other energy sources would tend to make the percentage difference in energy consumption somewhat less than the percentage difference in thennal conductivity. The second factoris related to the temperature imposed on the insulation during a thennal conductivity test as compared with the temperatures experienced by the insulation in an operating refrigerator. In a thermal conductivity test, the mean temperature ofthe insulation is usually 75°F, while the insulation in a refrigerator is at a lowertemperature. Thethermal conductivity of foam insulations vary with mean temperature, and different blowing gases give different temperature dependencies. The result is that the curves ofthennal conductivity versus temperature for two blowing agents may get closertogether (less percentage difference), farther apart (greater percentage difference), or cross over (reverse in sign ofpercent difference) as the temperature is lowered from 75°F to the mean temperatures typical ofrefrigerator operation. Reference 2 also gives results oftests conducted by the Home Appliance Department ofthe


### 4 electrical heaters. Finally, thennal conductivity measurements were made on samples ofthe foam insulation. Average results from the ARC tests are shownin Table 3. Table 4 gives the individual cabinet energy data from which the averages in Table 3 were derived. The results are given as percentage differences between data with the newblowing agent and datawith HCFC-141b. A positive value for thennal conductivity, cabinet energy, orreverse heat leakindicates a higher energy usage for the alternative blowing agent than for HCFC-14lb. Table 3 shows that the energy usage with cyclopentane would be about 10 percent higher thanwithHCFC-14lb, and that energy usage with carbon dioxide orHFC-134awould be morethan 10 percent greaterthan with HCFC-141b. HFC-245fa gave average energy usage and thennal conductivitythat were very comparable with HCFC-141b. Individual energy usages for HFC-245fawere both higher and lower than for HCFC-14lb. The other three new HFCs (236ea, 356mfc, and 365rnffm) had energy usages that were higherthan for HCFC-141b, butlowerthan for cyclopentane. Itwas noted that the fonnulations for the four newHFCs have notbeen optimized, while the commercially available technologies based on cyclopentane, HFC-134a, and carbon dioxide would presumably have been optimized. Even without optimization, the four newHFCs perfonned better than the three available technologies. In particular, it was noted that theHFC-365mfc, which had the highest energy usage ofthe four new HFCs, was fonnulated with a higherthan normal amount ofwater and that it would be expected to perform betterifless waterwere used in the formulation. While the thermal conductivity ofthe foam insulation is an indicator ofthe energy perfonnance of a refrigerator, the percentage change in thennal conductivity due to differences in blowing agent will not generally be the same as the percentage change in energy usage. This is because oftwo main factors. The first is that the heat leaks through theinsulated walls and doors ofa refrigerator/freezer are not the only sources ofenergyrequirementsfor the entire refrigerator. Other energy requirements arise from heat transfer around·door gaskets and at penetrations through the insulation, energy used for anti-sweat heaters, and energyused for the defrost cycle. These other energy sources would tend to make the percentage difference in energy consumption somewhat less than the percentage difference in thennal conductivity. The second factoris related to the temperature imposed on the insulation during a thennal conductivity test as compared with the temperatures experienced by the insulation in an operating refrigerator. In a thermal conductivity test, the mean temperature ofthe insulation is usually 75°F, while the insulation in a refrigerator is at a lowertemperature. Thethermal conductivity of foam insulations vary with mean temperature, and different blowing gases give different temperature dependencies. The result is that the curves ofthennal conductivity versus temperature for two blowing agents may get closertogether (less percentage difference), farther apart (greater percentage difference), or cross over (reverse in sign ofpercent difference) as the temperature is lowered from 75°F to the mean temperatures typical ofrefrigerator operation. Reference 2 also gives results oftests conducted by the Home Appliance Department ofthe


### 4Japanese Electrical Manufacturers Association (JEMA). These results are given in Table 5. The

energy usage with HFC-152a was higher than the ARC results with cyclopentane. The energy usage with HFC-236ea was comparable to the ARC results, but the energy usage with HFC-245fa (6 to 14%) was higher than the ARC results. The differences in HFC-245fa results between ARC and JEMA may be due to differences in the foam formulations. JEMA presented more recent data on alternative blowing agents at an ARC-ITAC/JEMA Workshop in June 1996, and will be presenting the same information at the International Conference on Ozone Protection Technologies (formerly the International CFC and Halon Alternatives Conference) in October, 1996. Results of thermal conductivity measurements on foam insulations at a mean temperature of 10°C (50°F) are given in Table 6, where the values are given relative to HCFC-141b. Again, cyclopentane-blown foam has a thermal conductivity about 10 percent higher than for HCFC-141b, while the four new HFCs have thermal conductivities that are 3 to 7 percent higher. They also performed energy measurements on refrigerator cabinets andfound that cabinets insulated with HFC-245fa used 3 to 6 percent more energy than with HCFC141b, and those insulated with HFC-236ea used 8 to 14 percent more than HCFC-141b. Researchers at Elf Atochem North America have reported values for thermal conductivity of polyurethane foam insulation blown with HCFC

- 141b, HFC-245fa, HFC-245ca, and HFC 365mfc.(8,9) Foams were blown entirely with these blowing agents and also with 50% with the blowing agent and 50% with carbon dioxide generated by water reacting with the isocyanate in the foam mix

. No optimizations of the formulations were made , and indeed, the thermal conductivity values appear to be high for all the blowing agents , including the HCFC-141b. Thermal conductivity was measured after blowing and then after aging for 30 days

. Table 7 gives the percentage difference relative to HCFC-141b for foam immediately after blowing. Other researchers have reported changes in foam thermal conductivity relative to HCFC-141b. SOLVAY ( 11) has reported an increase of 9.5 percent for HFC-365mfc

. Allied Signal (13) has reported an increase of 4.7 to 5.0 percent for HFC

-245fa

. Bayer ( 14) has reported an increase of 5.4 percent for polyurethane foam blown with HFC

-245fa. Bayer has also reported increases of 3.6 and 9.4 percent for polyisocyanurate foam blown with HFC-245fa and HFC-356mffm, respectively. MATERIALS COMPATIBILITY An acceptable foam blowing agent must be compatible with materials with which the foam insulation is in contact. The ARC is currently performing a test of the compatibility of a number of blowing agents with the different types of plastics that are used as the internal liner of refrigerators. Blowing agents included in these tests are cyclopentane, HFC-134a, HFC-236ea, HFC-245fa, and HCFC-141b (to act as a baseline). The tests will include thermal cycling of the liner and impact and adhesion tests. A report on progress on these tests will be given at the International Conference on Ozone Protection Technologies (formerly the International CFC and Halon Alternatives Conference) in October, 1996.

5 

# DRAET Japanese Electrical Manufacturers Association (JEMA). These results are given in Table 5. The energy usage withHFC-152a was higherthan the ARC results with cyclopentane. The energy usage with HFC-236ea was comparableto the ARC results, but the energyusage with HFC-245fa (6 to 14%) was higher than the ARC results. The differences in HFC-245faresults between ARC and JEMA may be due to differences in the foam formulations. JEMA presented more recent data on alternative blowing agents at an ARC-ITAC/JEMA Workshop in June 1996, and will be presentingthe same information at the International Conference on Ozone Protection Technologies (formerly the International CFC and Halon Alternatives Conference) in October, 1996. Results ofthermal conductivity measurements on foam insulations at a mean temperature ofIOoC (50°F) are given in Table 6, where the values are given relative to HCFC-141b. Again, cyclopentane-blown foam has a thermal conductivity about 10 percent higherthan for HCFC-141b, while the four new HFCs have thermal conductivities that are 3 to 7 percent higher. They also performed energy measurements on refrigerator cabinets and found that cabinets insulated with HFC-245faused 3 to 6 percent more energythan with HCFC14Ib, and thoSe insulated with HFC-236eaused 8 

### to 14 percent morethan HCFC-141b. Researchers at ElfAtochem North America have reported values for thermal conductivity of polyurethane foam insulation blown with HCFC-141b, HFC-245fa, HFC-245ca, and HFC365mfc.(8,9) Foams were blown entirely with these blowing agents and also with 50% with the blowing agent and 50% with carbon dioxide generated by water reacting with the isocyanate in the foam mix. No optimizations ofthe formulations were made, and indeed, the thermal conductivity values appearto be high for all the blowing agents, including theHCFC-141b. Thermal conductivity was measured afterblowing and then after aging for 30 days. Table 7 

### gives the percentage difference relative to HCFC-141b for foam immediately afterblowing. Other researchers have reported changes in foam thermal conductivity relative to HCFC-141b. SOLVAY (11) has reported an increase of9.5 percent for HFC-365mfc. Allied Signal (13) has reported an increase of4.7 

### to 5.0 percent for HFC-245fa. Bayer (14) has reported an increase of 5.4 percent for polyurethane foam blown with HFC-245fa. Bayer has also reported increases of 3.6 and 9.4 

### percent for polyisocyanurate foam blown with HFC-245fa and HFC-356mffm, respectively. MATERIALS COMPATIBILITY 

### An acceptable foam blowing agent must be compatible with materials with which the foam insulation is in contact. The ARC is currently performing a test ofthe compatibility ofa number ofblowing agents with the different types ofplastics that are used as the internal liner of refrigerators. Blowing agents included in these tests are cyclopentane, HFC-134a, HFC-236ea, HFC-245fa, and HCFC-141b (to act as a baseline). Thetests will include thermal cycling ofthe liner and impact and adhesion tests. A report on progress on these tests will be given at the International Conference on Ozone Protection Technologies (formerly the International CFC and Halon Alternatives Conference) in October, 1996.


### 5 

# DRAET Japanese Electrical Manufacturers Association (JEMA). These results are given in Table 5. The energy usage withHFC-152a was higherthan the ARC results with cyclopentane. The energy usage with HFC-236ea was comparableto the ARC results, but the energyusage with HFC-245fa (6 to 14%) was higher than the ARC results. The differences in HFC-245faresults between ARC and JEMA may be due to differences in the foam formulations. JEMA presented more recent data on alternative blowing agents at an ARC-ITAC/JEMA Workshop in June 1996, and will be presentingthe same information at the International Conference on Ozone Protection Technologies (formerly the International CFC and Halon Alternatives Conference) in October, 1996. Results ofthermal conductivity measurements on foam insulations at a mean temperature ofIOoC (50°F) are given in Table 6, where the values are given relative to HCFC-141b. Again, cyclopentane-blown foam has a thermal conductivity about 10 percent higherthan for HCFC-141b, while the four new HFCs have thermal conductivities that are 3 to 7 percent higher. They also performed energy measurements on refrigerator cabinets and found that cabinets insulated with HFC-245faused 3 to 6 percent more energythan with HCFC14Ib, and thoSe insulated with HFC-236eaused 8 

### to 14 percent morethan HCFC-141b. Researchers at ElfAtochem North America have reported values for thermal conductivity of polyurethane foam insulation blown with HCFC-141b, HFC-245fa, HFC-245ca, and HFC365mfc.(8,9) Foams were blown entirely with these blowing agents and also with 50% with the blowing agent and 50% with carbon dioxide generated by water reacting with the isocyanate in the foam mix. No optimizations ofthe formulations were made, and indeed, the thermal conductivity values appearto be high for all the blowing agents, including theHCFC-141b. Thermal conductivity was measured afterblowing and then after aging for 30 days. Table 7 

### gives the percentage difference relative to HCFC-141b for foam immediately afterblowing. Other researchers have reported changes in foam thermal conductivity relative to HCFC-141b. SOLVAY (11) has reported an increase of9.5 percent for HFC-365mfc. Allied Signal (13) has reported an increase of4.7 

### to 5.0 percent for HFC-245fa. Bayer (14) has reported an increase of 5.4 percent for polyurethane foam blown with HFC-245fa. Bayer has also reported increases of 3.6 and 9.4 

### percent for polyisocyanurate foam blown with HFC-245fa and HFC-356mffm, respectively. MATERIALS COMPATIBILITY 

### An acceptable foam blowing agent must be compatible with materials with which the foam insulation is in contact. The ARC is currently performing a test ofthe compatibility ofa number ofblowing agents with the different types ofplastics that are used as the internal liner of refrigerators. Blowing agents included in these tests are cyclopentane, HFC-134a, HFC-236ea, HFC-245fa, and HCFC-141b (to act as a baseline). Thetests will include thermal cycling ofthe liner and impact and adhesion tests. A report on progress on these tests will be given at the International Conference on Ozone Protection Technologies (formerly the International CFC and Halon Alternatives Conference) in October, 1996.


### 5TOXICITY

Allied-Signal has completed a number of toxicity tests on HFC-245fa.(13) These included acute dermal, acute inhalation screen, cardiac sensitization, human lympocyte, mouse micronucleus, Ames assay, and acute (4-hour) inhalation tests. Longer term, repeated dose studies are planned. Allied-Signal says that the results to date show that the toxicity ofHFC-245fa is as good as or better than that ofHCFC-141b. SOLVAY ( 11) has completed acute toxicity tests on HFC

-365mfc

. These included acute dermal, acute 6

-hour inhalation, and Ames tests

. As with the toxicity tests on HFC-245fa, the results of acute toxicity tests on HFC

-365mfc look promising. JEMA has performed "reverse-mutation assay in bacteria" and "chromosomal aberration tests" for HFC-245fa, HFC-236ea, HFC-245ca, and HFC-365mfc, and have found no negative toxicity data so far. Even though the results of acute toxicity tests are encouraging, they do not allow, any conclusion about the toxicological behavior under long-term, repeated dose conditions. Further work is needed to fully define the toxicological characteristics of the new HFC blowing agents. AVAILABILITY OF BLOWING AGENTS Of the new blowing agents, the one farthest along in development is HFC-245fa. Allied-Signal has publicly stated a commitment to develop HFC-245fa, and has a development schedule that could have product ready to meet the 2003 deadline.(13) The critical element is successful completion of toxicity testing. Suppliers of other HFCs are performing toxicity tests and are evaluating feasibilities, and have not yet made commitments to supply the chemicals. COMPRESSOR EFFICIENCY In order to meet increasing demands for energy efficiency of refrigerators, compressor manufacturers are developing more efficient compressors. Energy efficiency ratios (EERs) for the best currently available compressors are in the range of 5.4 to 5.5. (15) Ed Wuesthoff, Vice President of Engineering for Americold, estimates that the compressor EER will be about 5.8 by the year 2003. (16) This amounts to a 5 to 7 percent increase in compressor efficiency. This increase in compressor efficiency will translate into approximately a 3 to 4 percent increase in the overall coefficient of performance for the refrigeration cycle.(15) SUMMARY With the phaseout of HCFC-141b less than seven years away, the U.S. appliance industry is actively researching replacement blowing agents for the polyurethane foam insulation used in refrigerator/freezers. Potential replacement blowing agents presently being studied are
6 , '. 

# DRAEf

TOXICITY Allied-Signal has completed a number oftoxicity tests onHFC-245fa.(13) These included acute dermal, acute inhalation screen, cardiac sensitization, human lympocyte, mouse micronucleus, Ames assay, and acute (4-hour) inhalation tests. Longerterm, repeated dose studies are planned. Allied-Signal says that the results to date showthat the toxicity ofHFC-245fais as good as or betterthan that ofHCFC-I4Ib. SOLVAY (11) has completed acute toxicitytests onHFC-365rnfc

.. Theseincluded acute dermal, acute 6-hour inhal(l.tion, and Ames tests. As with the toxicitytests onHFC-245fa, the results of acute toxicity tests o'n HFC-365rnfc lookpromising. JEMA has performed "reverse-mutation assay in bacteria" and "chromosomal aberrationtests" for HFC-245fa, HFC-236ea, HFC-245ca, and HFC-365mfc, and have found no negative toxicity data so far. Even though the results ofacute toxicity tests are encouraging, they do not allowany conclusion about the toxicological behaviorunderlong-term, repeated dose conditions. Furtherwork is needed to fully define the toxicological characteristics ofthenewHFC blowing agents. 

### AVAILABILITY OFBLOWINGAGENTS Ofthe new blowing agents, the one farthest along in development is HFC-245fa. Allied-Signal has publicly stated a commitment to develop HFC-245fa, and has a development schedulethat could have product ready to meet the 2003 deadline.(13) The critical element is successful completion oftoxicity testing. Suppliers ofotherHFCs are performingtoxicitytests and are evaluating feasibilities, and have not yet made commitments to supplythe chemicals. 

### COMPRESSOREFFICIENCY In orderto meet increasing demands for energy efficiency ofrefrigerators, compress'or

. 

### - manufacturers are developing more efficient compressors. Energy efficiency ratios (EERs) for the best currently available compressors are in the range of5.4 to 5.5. (15) Ed Wuesthoff, Vice President ofEngineering for Americold, estimates that the compressorEERwill be about 5.8 by the year 2003. (16) This amounts to a 5 to 7 percentincrease in compressor efficiency. This increase in compressor efficiency will translate into approximately a 3 to 4 percent increase in the overall coefficient ofperformance for the refrigeration cycle.(I5) 

### SUMl\lARY With the phaseout ofHCFC-I4Ib less than seven years away, the U.S. appliance industry is actively researching replacement blowing agents for the polyurethane foam insulation used in refrigerator/freezers. Potential replacement blowing agents presentlybeing studied are

6 , '. 

# DRAEf

TOXICITY Allied-Signal has completed a number oftoxicity tests onHFC-245fa.(13) These included acute dermal, acute inhalation screen, cardiac sensitization, human lympocyte, mouse micronucleus, Ames assay, and acute (4-hour) inhalation tests. Longerterm, repeated dose studies are planned. Allied-Signal says that the results to date showthat the toxicity ofHFC-245fais as good as or betterthan that ofHCFC-I4Ib. SOLVAY (11) has completed acute toxicitytests onHFC-365rnfc

.. Theseincluded acute dermal, acute 6-hour inhal(l.tion, and Ames tests. As with the toxicitytests onHFC-245fa, the results of acute toxicity tests o'n HFC-365rnfc lookpromising. JEMA has performed "reverse-mutation assay in bacteria" and "chromosomal aberrationtests" for HFC-245fa, HFC-236ea, HFC-245ca, and HFC-365mfc, and have found no negative toxicity data so far. Even though the results ofacute toxicity tests are encouraging, they do not allowany conclusion about the toxicological behaviorunderlong-term, repeated dose conditions. Furtherwork is needed to fully define the toxicological characteristics ofthenewHFC blowing agents. 

### AVAILABILITY OFBLOWINGAGENTS Ofthe new blowing agents, the one farthest along in development is HFC-245fa. Allied-Signal has publicly stated a commitment to develop HFC-245fa, and has a development schedulethat could have product ready to meet the 2003 deadline.(13) The critical element is successful completion oftoxicity testing. Suppliers ofotherHFCs are performingtoxicitytests and are evaluating feasibilities, and have not yet made commitments to supplythe chemicals. 

### COMPRESSOREFFICIENCY In orderto meet increasing demands for energy efficiency ofrefrigerators, compress'or

. 

### - manufacturers are developing more efficient compressors. Energy efficiency ratios (EERs) for the best currently available compressors are in the range of5.4 to 5.5. (15) Ed Wuesthoff, Vice President ofEngineering for Americold, estimates that the compressorEERwill be about 5.8 by the year 2003. (16) This amounts to a 5 to 7 percentincrease in compressor efficiency. This increase in compressor efficiency will translate into approximately a 3 to 4 percent increase in the overall coefficient ofperformance for the refrigeration cycle.(I5) 

### SUMl\lARY With the phaseout ofHCFC-I4Ib less than seven years away, the U.S. appliance industry is actively researching replacement blowing agents for the polyurethane foam insulation used in refrigerator/freezers. Potential replacement blowing agents presentlybeing studied are

6cyclopentane, carbon dioxide, HFC-134a, HFC-236ea, HFC-245fa, HFC-356mffm, and HFC365mfc. While cyclopentane has been adopted for use as the blowing agent for refrigerators in Europe, there is reluctance for the U.S. refrigerator industry to adopt it immediately because of concerns about its higher energy usage, unknown toxicity risk from transfer to food, flammability risks during foam processing, and an environmental concern about volatile organic compounds. Cabinet energy tests showed that cyclopentane, carbon dioxide, and HFC-134a result in energy consumptions about 10 percent or more than that for HCFC-141b. These three blowing agents have been used commercially and are expected to be optimized. HFC-245fa gave an energy usage that was very comparable with HCFC-141b, and the other three new HFCs had energy usages that were higher than for HCFC-141b, but lower than for cyclopentane. Since the foam produced with the four new HFCs have not been optimized, there is potential for better performance than has been seen thus far. Tests of compatibility of the candidate blowing agents with plastic liners used in refrigerators are underway. Acute toxicity testing has been performed on HFC-245fa and HFC-365mfc. The results of these tests are encouraging, but long term, repeated dose tests are needed to fully characterize the toxological behavior. Of the new HFCs, only HFC-245fa has a supplier that has committed to develop and commercialize it. Potential suppliers of other third-generation blowing agents have not yet made such committments. Many new blowing agents are under study around the world, and it is possible that over the next few years some of them will emerge as viable candidates for replacing HCFC-14l b.
.REFERENCES 1. P. H. Howard, J. L. Tunkel, and R. V. Hendriks , "Identification of CFC and HCFC Substitutes for Blowing Polyurethane Foam Insulation Products," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 417-426 (October 1995). 2. G: J. Haworth, "Next Generation Insulation Foam Blowing Agents for Refrigerator/ Freezers," Proceedings, 47th Annual International Appliance Technical Conference, pp. 271-282 (May 1996). 3. V. Mariani and G

. Mersiadis, "For the Insulation of Domestic Refrigerators, the Use of CPentane has Become Almost An Industry Standard

. Its Use, However, Does Require Dedicated Machinery," Proceedings of Polyurethane 1995, pp

. 501-480, 1995. 4. A. J. Birch, V. Parenti, K.-J. Van Duin, G. F. Smits, and P. Clavel, "Iso-/n-pentane Blown Rigid Polyurethane Foam for Appliances: A Realistic and Economically Attractive Alternative to Cyclopentane," Proceedings of Polyurethane 1995, pp. 448-452, 1995. 

# DRAET
cyc!opentane, carbon dioxide, HFC-134a, HFC-236ea, HFC-245fa, HFC-356mffm, and HFC365mfc. While cyclopentane has been adopted for use as theblowing agent for refrigerators in Europe, there is reluctance for the U.S. refrigeratorindustryto adopt it immediatelybecause of concerns about its higher energy usage, unknown toxicityrisk from transferto food, flammability risks during foam processing, and an environmental concern about volatile organic compounds. Cabinet energy tests showed that cyc!opentane, carbon dioxide, and HFC-134a result in energy consumptions about 10 percent ormore thanthat forHCFC-141b. These three blowing agents have been used commercially and are expected to be optimized. HFC-245fa gave an energyusage that was very comparable with HCFC-141b, and the otherthree newHFCs had energyusages that were higherthan for HCFC-141b, but lower.than for cyclopentane. Sincethe foam produced with the four newHFCs have not been optimized, there is potential for betterperformancethan has been seen thus far. Tests ofcompatibility ofthe candidate blowing agents with plastic liners used in refrigerators are underway. Acute toxicity testing has been performed on HFC-245fa and HFC-365mfc. The results ofthese tests are encouraging, but long term, repeated dose tests are needed to fully characterizethe toxological behavior. Ofthe new HFCs, only HFC-245fa has a supplier that has committed to develop and commercialize it. Potential suppliers ofotherthird-generationblowing agents have not yet made such committments. Many new blowing agents are under study around the world, and it is possible that overthe next few years some ofthem

### will emerge as viable candidates for replacing HCFC-141b

.

.REFERENCES

1. P. H. Howard, J. L. Tunkel, and R. V. Hendriks, IIIdentification ofCFC and HCFC Substitutes for Blowing Polyurethane Foam InsulationProducts:' Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 417-426 (October 1995). 2. G. J. Haworth, IINext Generation Insulation FoamBlowing Agents for RefrigeratorlFreezers, II Proceedings, 47th Annual International Appliance Technical Conference, pp. 271-282 (May 1996). 3. V. Mariani and G. Mersiadis, "Forthe Insulation ofDomesticRefrigerators, theUse ofCPentane has Become Almost An Industry Standard. Its Use, However, DoesRequire Dedicated Machinery," Proceedings ofPolyurethane 1995, pp. 501-480, 1995. 4. A. J. Birch, V. Parenti, K.-J. Van Duin, G. F. Smits, and P. Clavel, "Iso-/n-pentaneBlown Rigid Polyurethane Foam for Appliances: A Realistic and Economically Attractive Alternative to Cyc!opentane," Proceedings ofPolyurethane 1995, pp. 448-452, 1995.

7 

# DRAET
cyc!opentane, carbon dioxide, HFC-134a, HFC-236ea, HFC-245fa, HFC-356mffm, and HFC365mfc. While cyclopentane has been adopted for use as theblowing agent for refrigerators in Europe, there is reluctance for the U.S. refrigeratorindustryto adopt it immediatelybecause of concerns about its higher energy usage, unknown toxicityrisk from transferto food, flammability risks during foam processing, and an environmental concern about volatile organic compounds. Cabinet energy tests showed that cyc!opentane, carbon dioxide, and HFC-134a result in energy consumptions about 10 percent ormore thanthat forHCFC-141b. These three blowing agents have been used commercially and are expected to be optimized. HFC-245fa gave an energyusage that was very comparable with HCFC-141b, and the otherthree newHFCs had energyusages that were higherthan for HCFC-141b, but lower.than for cyclopentane. Sincethe foam produced with the four newHFCs have not been optimized, there is potential for betterperformancethan has been seen thus far. Tests ofcompatibility ofthe candidate blowing agents with plastic liners used in refrigerators are underway. Acute toxicity testing has been performed on HFC-245fa and HFC-365mfc. The results ofthese tests are encouraging, but long term, repeated dose tests are needed to fully characterizethe toxological behavior. Ofthe new HFCs, only HFC-245fa has a supplier that has committed to develop and commercialize it. Potential suppliers ofotherthird-generationblowing agents have not yet made such committments. Many new blowing agents are under study around the world, and it is possible that overthe next few years some ofthem

### will emerge as viable candidates for replacing HCFC-141b

.

.REFERENCES

1. P. H. Howard, J. L. Tunkel, and R. V. Hendriks, IIIdentification ofCFC and HCFC Substitutes for Blowing Polyurethane Foam InsulationProducts:' Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 417-426 (October 1995). 2. G. J. Haworth, IINext Generation Insulation FoamBlowing Agents for RefrigeratorlFreezers, II Proceedings, 47th Annual International Appliance Technical Conference, pp. 271-282 (May 1996). 3. V. Mariani and G. Mersiadis, "Forthe Insulation ofDomesticRefrigerators, theUse ofCPentane has Become Almost An Industry Standard. Its Use, However, DoesRequire Dedicated Machinery," Proceedings ofPolyurethane 1995, pp. 501-480, 1995. 4. A. J. Birch, V. Parenti, K.-J. Van Duin, G. F. Smits, and P. Clavel, "Iso-/n-pentaneBlown Rigid Polyurethane Foam for Appliances: A Realistic and Economically Attractive Alternative to Cyc!opentane," Proceedings ofPolyurethane 1995, pp. 448-452, 1995.

7

# DRAF3.,

5. S. Mirasol, D. Bhattacharjee, and S. J. Williams, "100% CO2 Blown Class I* Flame Rated Polyurethane Foam," Proceedings of Polyurethane 1995, pp. 47-50, 1995. 6. H. J. M. Grunbauer, L. Cikut, and G. J. Haworth, " Improved Aging CO2 Blown Foam for Refrigerators/Freezers," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 463-472 (October 1995). 7. C. Fiorentini, M. Taverna, and J. Luca, "Liquid-Carbon-Dioxide-Blown Molded Foams: the Technology and Initial Applications," Proceedings of Polyurethane 1995, pp. 476-480 (1995). 8. J. Murphy and J. Costa, "An Examination of Liquid and Gaseous Fluorochemicals for Foam Insulation - Part II," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 428-437 (October 1995). 9. J. Murphy and J

. Costa, "An Examination of Liquid & Gaseous Fluorochemicals for Foam Insulation - Part II," Proceedings of Polyurethane 1995, pp

. 39-45, 1995. 10. J. D. Roux, A. Albouy, J. Murphy, and J. Costa, "Recent Developments in Zero ODP Blowing Agents for Rigid Polyurethane Foams," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 448-452 (October 1995). 11. P. P. Barthelemy and A. Leroy, "Latest Results in the Development of Next Generation HFC Blowing Agents," Proceedings of Polyurethane 1995, pp. 26-33, 1995. 12. K. Ashida, K. Morimoto, and A. Yufu, "Zero ODP , Halogen-free Azeotropes as Blowing Agents for Plastic Foams," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 438-447 (October 1995). 13. D. J. Williams, M. C. Bogdan, R. C. Parker, and G. M. Knopeck, "Update on the Development of HFC-245fa as a Liquid HFC Blowing Agent," Proceedings of Polyurethane 1995, pp. 2-9, 1995. 14. F. C. Rossitto and M. E. McGregor, "Evaluation of HFC Blowing Agents in Continuous and Discontinuous Panel Formulations," Proceedings of Polyurethane 1995, pp. 182-185, 1995. 15. Private communication from E . A. Vineyard (ORNL) to K. E

. Wilkes (August 21, 1996). 16. Private communication from E. Wuesthoff (Americold) to E. A. Vineyard (ORNL), (August, 1996). Americold is a major manufacturer of compressors for refrigerators.

8 

# DRA

5. S. Mirasol, D. BhattachaIjee, and S. J. Williams, "100% CO2 Blown Class 1* Flame Rated Polyurethane Foam," Proceedings ofPolyurethane 1995, pp. 47-50, 1995. 6. H. J. M. Grilnbauer, L. Cikut, and G. J. Haworth, "Improved Aging CO2 BlownFoamfor RefrigeratorslFreezers," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 463-472 (October 1995). 7. 

### C. Fiorentini, M. Taverna, and J. Luca, "Liquid-Carbon-Dioxide-BlownMolded Foams: the Technology and Initial Applications," Proceedings ofPolyurethane 1995, pp. 476-480 (1995). 8. J. Murphy and J. Costa, 

### "An Examination ofLiquid and GaseousFluorochemicals for Foam Insulation

- PartII," Proceedings, 1995 International CFC and HalonAlternatives Conference, pp. 428-437 (October 1995). 9. 

### J. Murphy and J. Costa, 

### "An Examination ofLiquid & Gaseous Fluorochemicals for Foam Insulation

- Part II," Proceedings ofPolyurethane 1995, pp. 39-45, 1995. 10. 

### J. D. Roux, 

### A. Albouy, J. Murphy, and 

### J. Costa, "RecentDevelopments in Zero ODP Blowing Agents for Rigid PolyurethaneFoams," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 448-452 (October 1995). 11. P. P. Barthelemy and 

### A. Leroy, "Latest Results in the Development ofNext Generation

### HFC Blowing Agents," Proceedings ofPolyurethane 1995, pp. 26-33, 1995. 12. K. Ashida, K. Morimoto, and 

### A. Yufu, "Zero ODP, Halogen-free Azeotropes as Blowing Agents for Plastic Foams," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 438-447 (October 1995). 13. D. J. Williams, M. C. Bogdan, R. 

### C. Parker, and G. M. Knopeck, "Update on the Development ofHFC-245fa as a Liquid HFC Blowing Agent, II Proceedings ofPolyurethane 1995, pp. 2-9, 1995. 14. F. C. Rossitto and M. E. McGregor, "Evaluation ofHFC Blowing Agents in Continuous and Discontinuous Panel Formulations," Proceedings ofPolyurethane 1995, pp. 182-185, 1995. 15. Private communication from E. 

### A. Vineyard (ORNL) to K. E. Wilkes (August 21,1996). 16. Private communication from E. Wuesthoff(Americold) to E. A. Vineyard (ORNL), (August, 1996). Americold is a major manufacturer ofcompressors for refrigerators.

8 

# DRA

5. S. Mirasol, D. BhattachaIjee, and S. J. Williams, "100% CO2 Blown Class 1* Flame Rated Polyurethane Foam," Proceedings ofPolyurethane 1995, pp. 47-50, 1995. 6. H. J. M. Grilnbauer, L. Cikut, and G. J. Haworth, "Improved Aging CO2 BlownFoamfor RefrigeratorslFreezers," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 463-472 (October 1995). 7. 

### C. Fiorentini, M. Taverna, and J. Luca, "Liquid-Carbon-Dioxide-BlownMolded Foams: the Technology and Initial Applications," Proceedings ofPolyurethane 1995, pp. 476-480 (1995). 8. J. Murphy and J. Costa, 

### "An Examination ofLiquid and GaseousFluorochemicals for Foam Insulation

- PartII," Proceedings, 1995 International CFC and HalonAlternatives Conference, pp. 428-437 (October 1995). 9. 

### J. Murphy and J. Costa, 

### "An Examination ofLiquid & Gaseous Fluorochemicals for Foam Insulation

- Part II," Proceedings ofPolyurethane 1995, pp. 39-45, 1995. 10. 

### J. D. Roux, 

### A. Albouy, J. Murphy, and 

### J. Costa, "RecentDevelopments in Zero ODP Blowing Agents for Rigid PolyurethaneFoams," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 448-452 (October 1995). 11. P. P. Barthelemy and 

### A. Leroy, "Latest Results in the Development ofNext Generation

### HFC Blowing Agents," Proceedings ofPolyurethane 1995, pp. 26-33, 1995. 12. K. Ashida, K. Morimoto, and 

### A. Yufu, "Zero ODP, Halogen-free Azeotropes as Blowing Agents for Plastic Foams," Proceedings, 1995 International CFC and Halon Alternatives Conference, pp. 438-447 (October 1995). 13. D. J. Williams, M. C. Bogdan, R. 

### C. Parker, and G. M. Knopeck, "Update on the Development ofHFC-245fa as a Liquid HFC Blowing Agent, II Proceedings ofPolyurethane 1995, pp. 2-9, 1995. 14. F. C. Rossitto and M. E. McGregor, "Evaluation ofHFC Blowing Agents in Continuous and Discontinuous Panel Formulations," Proceedings ofPolyurethane 1995, pp. 182-185, 1995. 15. Private communication from E. 

### A. Vineyard (ORNL) to K. E. Wilkes (August 21,1996). 16. Private communication from E. Wuesthoff(Americold) to E. A. Vineyard (ORNL), (August, 1996). Americold is a major manufacturer ofcompressors for refrigerators.

8Table 1

. Industry Representation in Appliance Research Consortium

Refrigerator/freezer manufacturers Amana Frigidaire General Electric Marvel Maytag Sanyo Sub-Zero W. C. Wood Whirlpool Potential blowing agent suppliers Allied-Signal DuPont Elf Atochem ICI Foam chemical suppliers Air Products BASF Bayer Dow Chemical Goldschmidt Chemical ICI Plastic suppliers BASF Bayer Dow Chemical G. E. Plastics 

# DRAEJ

Table 1. IndustryRepresentation in Appliance Research Consortium

• Refiigerator/freezermanufacturers Amana Frigidaire General Electric Marvel Maytag Sanyo Sub-Zero W. C. Wood Whirlpool

• Potential blowing agent suppliers Allied-Signal DuPont ElfAtochem ICI

• Foam chemical suppliers 

### AirProducts BASF Bayer Dow Chemical Goldschmidt Chemical ICI

• Plastic suppliers BASF Bayer Dow Chemical G. E. Plastics

9 

# DRAEJ

Table 1. IndustryRepresentation in Appliance Research Consortium

• Refiigerator/freezermanufacturers Amana Frigidaire General Electric Marvel Maytag Sanyo Sub-Zero W. C. Wood Whirlpool

• Potential blowing agent suppliers Allied-Signal DuPont ElfAtochem ICI

• Foam chemical suppliers 

### AirProducts BASF Bayer Dow Chemical Goldschmidt Chemical ICI

• Plastic suppliers BASF Bayer Dow Chemical G. E. Plastics

9

# DRAFT

Table 2. Blowing Agents Under Active Study by the U. S. and Japanese Refrigerator Industries as Replacements for HCFC-141b Industry Name Chemical Name Syracuse/ EPA Rank Cyclopentane Cyclopentane 13 Carbon dioxide Carbon dioxide Not listed HFC-134a 1,1,1,2-Tetrafluoroethane 79 HFC-152a 1,1-Difluoroethane 68 HFC-236ea 1, 1, 1,2,3,3-Hexafluoropropane 75 HFC-245ca 1, 1,2,2,3-Pentafluoropropane 9 HFC-245fa 1, 1, 1,3,3-Pentafluoropropane 32 HFC-3 56mffm 1, 1, 1,4,4,4-Hexafluorobutane 21 HFC-365mfc 1,1,1,3,3-Pentafluorobutane Not listed

10 

# DRAB

Table 2. Blowing Agents Under Active Studyby the U.S. and Japanese RefrigeratorIndustries as Replacements forHCFC-141b IndustryName Chemical Name SyracuselEPA Rank CycIopentane CycIopentane 13 Carbon dioxide Carbon dioxide Not listed HFC-134a 1,1,1,2-Tetrafluoroethane 79 HFC-152a 1,1-Difluoroethane 68 HFC-236ea 1,I, 1,2,3,3-Hexafluoropropane 75 HFC-245ca 1,1,2,2,3-Pentafluoropropane 9 HFC-245fa 1,1,1,3,3

-Pentafluoropropane 32 HFC-356mffm 1, 1, 1,4,4,4-Hexafluorobutane 21 HFC-365mfc 1, 1, 1,3,3-Pentafluorobutane Notlisted

10 

# DRAB

Table 2. Blowing Agents Under Active Studyby the U.S. and Japanese RefrigeratorIndustries as Replacements forHCFC-141b IndustryName Chemical Name SyracuselEPA Rank CycIopentane CycIopentane 13 Carbon dioxide Carbon dioxide Not listed HFC-134a 1,1,1,2-Tetrafluoroethane 79 HFC-152a 1,1-Difluoroethane 68 HFC-236ea 1,I, 1,2,3,3-Hexafluoropropane 75 HFC-245ca 1,1,2,2,3-Pentafluoropropane 9 HFC-245fa 1,1,1,3,3

-Pentafluoropropane 32 HFC-356mffm 1, 1, 1,4,4,4-Hexafluorobutane 21 HFC-365mfc 1, 1, 1,3,3-Pentafluorobutane Notlisted

10

# DRAFT

Table 3. Results of ARC Tests of Replacement Blowing Agents.

Results are relative to HCFC-141b. Blowing Agent Thermal Conductivity Cabinet Energy Reverse Heat Leak Cyclopentane +11.9% +9.6%

- HFC-134a +16.8% +13.6%
- Carbon dioxide +16.9% +12.1%

- HFC-356mffm +5.3 to +7.0% +3.69% +3.11% HFC-245fa -1.8 to 0.0% +0.90% -0.64% HFC-236ea +4.0 to +7.6% +3.08% 0.52% HFC-365mfc +7.9 to +11.6% +7.37% +8.14% Cyclopentane +9.1 to +10.3% +8.78% +6.71%

Table 4. Individual Cabinet Energies from ARC Tests Results are Relative to HCFC-141b Blowing Agent Cabinet Energy Cyclopentane +6.6%,+9.2%,+11.3%,+10.0%,+11.0%,+9.6% HFC-134a +15.8%,+6.5%,+18.5% Carbon dioxide +12.1% HFC-365mffm +2.5%,+3.1%,+4.7%,+5.5%,+2.7% HFC-245fa +1.1%,+9.2%,-8.8%,+4.4%,-0.8% HFC-236ea +3.4%,+0.9%,+3.2%,+7.1%,+1:0% HFC-365mfc +5.2%0,+4.6%,+11.7%,+10.0%,+5.4% Cyclopentane +9.2%,+9.1%,+6.3%,+12.2%,+7.2%

11 Blowing Agent Cyclopentane HFC-134a Carbon dioxide HFC-356mffm HFC-245fa HFC-236ea HFC-365mfc Cyclopentane

Blowing Agent Cyc!opentane HFC-134a Carbon dioxide HFC-365mffm HFC-245fa HFC-236ea HFC-365mfc Cyclopentane 

# DRAET

Table 3. Results ofARC Tests ofReplacementBlowing Agents. Results are relative to HCFC-141b.
Thermal Conductivity CabinetEnergy +11.9% +9.6% +16.8% +13.6% +16.9% +12.1% +5.3 to +7.0% +3.69% -1.8 to 0.0% +0.90% +4.0 to +7.6% +3.08% +7.9 to +11.6% +7.37% +9.1 to +10.3% +8.78%

Table 4. Individual Cabinet Energies from ARC Tests Results are Relative to HCFC-141b
Cabinet Energy ReverseHeatLeak



# -

-

- +3.11% -0.64% 0.52% +8.14% +6.71%

+6.6%,+9.2%,+ 11.3%,+ 1 0.0%,+11.0%,+9.6%
+15.8%,+6.5%,+18.5% +12.1% +2.5%,+3.1%,+4.7%,+5.5%,+2.7%
+1.1%,+9.2%,-8.8%,+4.4%,-0.8% +3.4%,+0.9%,+3.2%,+7.1%,+1:0% +5.2%,+4.6%,+11.7%,+10.0%,+5.4% +9.2%,+9.1%,+6.3%,+12.2%,+7.2%

11 Blowing Agent Cyclopentane HFC-134a Carbon dioxide HFC-356mffm HFC-245fa HFC-236ea HFC-365mfc Cyclopentane

Blowing Agent Cyc!opentane HFC-134a Carbon dioxide HFC-365mffm HFC-245fa HFC-236ea HFC-365mfc Cyclopentane 

# DRAET

Table 3. Results ofARC Tests ofReplacementBlowing Agents. Results are relative to HCFC-141b.
Thermal Conductivity CabinetEnergy +11.9% +9.6% +16.8% +13.6% +16.9% +12.1% +5.3 to +7.0% +3.69% -1.8 to 0.0% +0.90% +4.0 to +7.6% +3.08% +7.9 to +11.6% +7.37% +9.1 to +10.3% +8.78%

Table 4. Individual Cabinet Energies from ARC Tests Results are Relative to HCFC-141b
Cabinet Energy ReverseHeatLeak



# -

-

- +3.11% -0.64% 0.52% +8.14% +6.71%

+6.6%,+9.2%,+ 11.3%,+ 1 0.0%,+11.0%,+9.6%
+15.8%,+6.5%,+18.5% +12.1% +2.5%,+3.1%,+4.7%,+5.5%,+2.7%
+1.1%,+9.2%,-8.8%,+4.4%,-0.8% +3.4%,+0.9%,+3.2%,+7.1%,+1:0% +5.2%,+4.6%,+11.7%,+10.0%,+5.4% +9.2%,+9.1%,+6.3%,+12.2%,+7.2%

119..
Table 5. Results of JEMA Energy Consumption Tests

Results are relative to HCFC-141b. Blowing Agent Energy Penalty HFC-152a +17% HFC-236ea +4% HFC-245ca +4% HFC-245fa +6% to +14% HFC-356mffm No baseline HCFC-141b data for comparison.

Table 6. Results of JEMA Thermal Conductivity Tests Results are relative to HCFC-141b, and apply to a 50°F mean temperature. Blowing Agent Thermal Conductivity Increase HFC-245fa +3.1% HFC-236ea +5.6% HFC-245ca +4.3% HFC-356mffm +6.8% Cyclopentane +9.9%
Table 7. Results of Elf Atochem Thermal Conductivity Tests Immediately after Blowing Results are relative to HCFC-141b. Blowing Agent Blown 100% with blowing agent Blown with 50% CO2 

### HFC-245fa +3.8% HCFC-141b data questionable HFC-245ca + 1.6% +6.3% HFC-365mfc
- 1.1%, -4.9% +2.3%

12 Blowing Agent HFC-152a HFC-236ea HFC-245ca HFC-245fa HFC-356mffm 

# DRAEaTt

.. Table 5. Results ofJEMAEnergy Consumption Tests Results are relative to HCFC-141b. EnergyPenalty +17% +4% +4% +6% to +14% No baseline HCFC-141b data for comparison.

Table 6. Results ofJEMA Thermal Conductivity Tests Results are relative to HCFC-141b, and apply to a 50°F mean temperature. BlowingAgent Thermal Conductivity Increase HFC-245fa +3.1% HFC-236ea +5.6% HFC-245ca +4.3% HFC-356mffm +6.8% Cyciopentane +9.9%

Table 

### 7. Results ofElfAtochem Thermal Conductivity Tests Immediately afterBlowing Results are relative to HCFC-141b. Blowing Agent Blown 100% with blowing agent Blown with 50% CO2 HFC-245fa +3.8% HCFC-141b data questionable HFC-245ca +1.6% +6.3% HFC-365mfc -1.1%, -4.9% +2.3%

12 Blowing Agent HFC-152a HFC-236ea HFC-245ca HFC-245fa HFC-356mffm 

# DRAEaTt

.. Table 5. Results ofJEMAEnergy Consumption Tests Results are relative to HCFC-141b. EnergyPenalty +17% +4% +4% +6% to +14% No baseline HCFC-141b data for comparison.

Table 6. Results ofJEMA Thermal Conductivity Tests Results are relative to HCFC-141b, and apply to a 50°F mean temperature. BlowingAgent Thermal Conductivity Increase HFC-245fa +3.1% HFC-236ea +5.6% HFC-245ca +4.3% HFC-356mffm +6.8% Cyciopentane +9.9%

Table 

### 7. Results ofElfAtochem Thermal Conductivity Tests Immediately afterBlowing Results are relative to HCFC-141b. Blowing Agent Blown 100% with blowing agent Blown with 50% CO2 HFC-245fa +3.8% HCFC-141b data questionable HFC-245ca +1.6% +6.3% HFC-365mfc -1.1%, -4.9% +2.3%

12

# CRAFT

APPENDIX A RANKING OF THIRD GENERATION BLOWING AGENTS BY

SYRACUSE RESEARCH CORPORATION

AND ENVIRONMENTAL PROTECTION AGENCY

13 

# 'DRAfT

APPENDIX A RANKING OFTHIRD GENERATIONBLOWINGAGENTS BY SYRACUSE RESEARCH CORPORATION AND ENVIRONMENTAL PROTECTIONAGENCY

13 

# 'DRAfT

APPENDIX A RANKING OFTHIRD GENERATIONBLOWINGAGENTS BY SYRACUSE RESEARCH CORPORATION AND ENVIRONMENTAL PROTECTIONAGENCY

13Rank Name Overall GWP MW TC BP Cyclopentene 1 2 9 24 52 1,4-Pentadiene 2 8 10 68 7 1-Butene, 2-methyl- 3 3 13 76 20 3-Flourocyclobutene 4 6 17 67 25 2-Pentene 5 4 12 70 34 1-Pentene 6 10 14 86 18 Butane, 1-fluoro- 7 28 22 65 23 2-Butene, 2-methyl- 8 1 15 93 30 1,1,2,2,3-Pentafluoropropane 9 59 69 9 5 1-Butene, 3,3-dimethyl- 10 12 26 61 44 Butane, 2-methyl 11 21 18 97 11 2-Butene 12 5 3 83 58 Cyclopentane 13 18 11 54 68 1,1,1,2,3-Pentafluoropropane 14 70 70 10 4 Difluoromethyl fluoromethly ether 15 73 43 21 17 1-Pentene, 4-methyl- 16 11 25 43 76 1,2-Difluorocyclobutane 17 49 34 73 1 1,4-Difluorobutane 18 30 38 77 14 Fluorocyclobutane 19 43 20 85 15 1,1-Difluoroacetone 20 68 36 32 28 1,1,1,4,4,4-Hexafluorobutane 21 56 92 14 3 2-Propanone, 1,1,3,3-tetrafluoro- 22 87 62 16 2 1,1-Difluorocyclobutane 23 40 35 74 19 GWP = global warming potential; MW = molecular weight; TC = thermal conductivity; BP = boiling point
14 

# ORA 

# J

Rank Name MW TC Overall GWP Cyclopentene 1 2 9 24 1,4-Pentadiene 2 8 10 68 I-Butene, 2-methyl- 3 3 13 76 3 -Flourocyclobutene 4 6 17 67 2-Pentene 5 4 12 70 I-Pentene 6 10 14 86 Butane, I-fluoro- 7 28 22 65 2-Butene, 2-methyl- 8 1 15 93 1,1,2,2,3-Pentafluoropropane 9 59 69 9 I-Butene, 3,3-dimethyl- 10 12 26 61 Butane, 2-methyl 11 21 18 97 2-Butene 12 5 3 83 Cyclopentane 13 18 11 54 1,1,I,2,3-Pentafluoropropane 14 70 70 10 Difluoromethyl fluoromethly ether 15 73 43 21 I-Pentene,4-methyl- 16 11 25 43 1,2-Diflllorocyclobutane 17 49 34 73 1,4-Diflllorobutane 18 30 38 77 Fluorocyc1obutane 19 43 20 85 l,l-Difluoroacetone 20 68 36 32 1, 1, 1,4,4,4-Hexafluorobutane 21 56 92 14 2-Propanone, 1,1,3,3-tetrafluoro- 22 87 62 16 I,I-Difluorocyclobutane 23 40 35 74 GWP = global warmmg potentIal; MW = molecular weight; TC = thermal conductivity; BP = boiling point
14 BP 52 7 20 25 34 18 23 30 5 44 11 58 68 4 17 76

1 14 15 28 3 2 19 

# ORA 

# J

Rank Name MW TC Overall GWP Cyclopentene 1 2 9 24 1,4-Pentadiene 2 8 10 68 I-Butene, 2-methyl- 3 3 13 76 3 -Flourocyclobutene 4 6 17 67 2-Pentene 5 4 12 70 I-Pentene 6 10 14 86 Butane, I-fluoro- 7 28 22 65 2-Butene, 2-methyl- 8 1 15 93 1,1,2,2,3-Pentafluoropropane 9 59 69 9 I-Butene, 3,3-dimethyl- 10 12 26 61 Butane, 2-methyl 11 21 18 97 2-Butene 12 5 3 83 Cyclopentane 13 18 11 54 1,1,I,2,3-Pentafluoropropane 14 70 70 10 Difluoromethyl fluoromethly ether 15 73 43 21 I-Pentene,4-methyl- 16 11 25 43 1,2-Diflllorocyclobutane 17 49 34 73 1,4-Diflllorobutane 18 30 38 77 Fluorocyc1obutane 19 43 20 85 l,l-Difluoroacetone 20 68 36 32 1, 1, 1,4,4,4-Hexafluorobutane 21 56 92 14 2-Propanone, 1,1,3,3-tetrafluoro- 22 87 62 16 I,I-Difluorocyclobutane 23 40 35 74 GWP = global warmmg potentIal; MW = molecular weight; TC = thermal conductivity; BP = boiling point
14 BP 52 7 20 25 34 18 23 30 5 44 11 58 68 4 17 76

1 14 15 28 3 2 19Rank Name 

### Overall GWP MW TC BP Pentane 24 20 19 98 33 1-Propene, 3,3,3-trifluoro- 25 13 41 27 90 Cyclobutane 26 36 5 99 31 Trifluoromethoxymethoxymethane 27 24 61 75 16 1,2,3-Trifluorocyclobutane 28 58 48 59 12 2-Propanone 29 53 7 38 81 Cyclopropane, ethyl- 30 32 16 103 29 1,4-Pentadiene, 3-methyl- 31 7 24 71 79 1,1,1,3,3-Pentafluoropropane 32 77 71 13 21 Dimethoxymethane 33 16 21 101 45 Butane, 2,3-dimethyl- 34 17 27 60 83 Cyclopropane, methyl- 35 50 4 84 51 1,1,2,2,3,3,-Hexafluorocyclopentane 36 29 97 37 27 1,1-Difluorobutane 37 31 40 79 40 Trimethylene oxide 38 22 6 92 70 2-Propanone, 1,1,1-trifluoro- 39 86 50 46 9 1,1,1-Trifluorobutane 40 33 49 49 60 1,1-Difluorocyclopentane 41 19 47 69 57 1,1,2,2-Tetrafluoropropane 42 54 53 23 65 1,2,3,4-Tetrofluorocyclobutane 43 72 58 39 26 1,1,2,2-Tetrafluoroethyl ethyl ether 44 38 76 57 24 Methane, iododifluoro- 45 93 96 2 6 1,2-Difluorobutane 46 41 39 78 39

15 , .'

# DRA~T

Rank Name Overall GWP MW TC 

### BP Pentane 24 20 19 98 33 I-Propene,3,3,3-trifluoro- 25 13 41 27 90 Cyclobutane 26 36 5 99 31 Trifluoromethoxymethoxymethane 27 24 61 75 . 16 1,2,3-Trifluorocyclobutane 28 58 48 59 12 2-Propanone 29 53 7 38 81 Cyclopropane, ethyl- 30 32 16 103 29 I,4-Pentadiene,3-methyl- 31 7 24 71 79 I,l,I,3,3-Pentafluoropropane 32 77 71 13 21 Dimethoxymethane 33 16 21 101 45 Butane, 2,3-dimethyl- 34 17 27 60 83 Cyclopropane, methyl- 35 50 4 84 51 I,I,2,2,3,3,-Hexafluorocyclopentane 36 29 97 37 27 I,I-Difluorobutane 37 31 40 79 40 Trimethylene oxide 38 22 6 92 70 2-Propanone, 1,1,I-trifluoro- 39 86 50 46 9 1,1,1-Trifluorobutane 40 33 49 49 60 1,I-Difluorocyclopentane 41 19 47 69 57 1,1,2,2-Tetrafluoropropane 42 54 53 23 65 1,2,3,4-Tetrofluorocyclobutane 43 72 58 39 26 1,1,2,2-Tetrafluoroethyl ethyl ether 44 38 76 57 24 Methane, iododifluoro- 45 93 96 2 6 1,2-Difluorobutane 46 41 39 78 39

15 , .'

# DRA~T

Rank Name Overall GWP MW TC 

### BP Pentane 24 20 19 98 33 I-Propene,3,3,3-trifluoro- 25 13 41 27 90 Cyclobutane 26 36 5 99 31 Trifluoromethoxymethoxymethane 27 24 61 75 . 16 1,2,3-Trifluorocyclobutane 28 58 48 59 12 2-Propanone 29 53 7 38 81 Cyclopropane, ethyl- 30 32 16 103 29 I,4-Pentadiene,3-methyl- 31 7 24 71 79 I,l,I,3,3-Pentafluoropropane 32 77 71 13 21 Dimethoxymethane 33 16 21 101 45 Butane, 2,3-dimethyl- 34 17 27 60 83 Cyclopropane, methyl- 35 50 4 84 51 I,I,2,2,3,3,-Hexafluorocyclopentane 36 29 97 37 27 I,I-Difluorobutane 37 31 40 79 40 Trimethylene oxide 38 22 6 92 70 2-Propanone, 1,1,I-trifluoro- 39 86 50 46 9 1,1,1-Trifluorobutane 40 33 49 49 60 1,I-Difluorocyclopentane 41 19 47 69 57 1,1,2,2-Tetrafluoropropane 42 54 53 23 65 1,2,3,4-Tetrofluorocyclobutane 43 72 58 39 26 1,1,2,2-Tetrafluoroethyl ethyl ether 44 38 76 57 24 Methane, iododifluoro- 45 93 96 2 6 1,2-Difluorobutane 46 41 39 78 39

15Rank Name 

### Overall GWP MW TC BP 1,1,2,3,3-Pentafluoropropane 47 83 68 6 41 1,1,1,3-Tetrafluoroacetone 48 90 60 36 13 Methyl trifluoroacetate 49 71 57 26 49 1,1,2,2,3,3-Hexafluoropropane 50 75 82 12 35 Butane, 2,2-dimethyl- 51 26 28 81 69 1,2,3-Trifluorocyclopentane 52 35 56 52 62 Tetramethyl silane 53 63 33 102 8 1,1,2,2-Tetrafluorocyclobutane 54 44 59 45 59 1,1,2,3,4,4-Hexafluoro-l-butene 55 14 88 34 72 2-Propanone, 1,1,1,3,3-pentafluoro- 56 96 77 15 22 Propane, 1,1,1-trifluoro- 57 51 42 31 86 Trifluoromethyl ethyl ether 58 39 52 63 56 1,3-Difluoroacetone 59 60 37 48 67 1,1,3,3-Tetrafluorooxetane 60 82 63 58 10 1,2-Difluorocyclopentane 61 27 46 66 74 1-Trifluoromethoxy-2-fluoroethane 62 42 67 55 50 1-Fluoro-2-ethylcyclopropane 63 34 31 95 54 1-Propene, 1,1,2,3,3,3-hexafluoro- 64 15 81 22 97 1-Methoxy-2,2,2-trifluoroethane 65 48 51 62 55 Fluorocyclopentane 66 23 29 82 82 Bis-2,2,2-trifluoroethyl ether 67 64 99 17 38 Ethane, 1,1-difluoro- 68 76 8 40 94 1,2,3,4-Tetrafluorocyclopentane 69 47 74 53 47

16 r.

Rank Name Overall GWP 

### MW Te BP 1,1,2,3,3-Pentafluoropropane 47 83 68 6 41 1,1,1,3

-Tetrafluoroacetone 48 90 60 36 13 Methyl trifluoroacetate 49 71 57 26 49 I,I,2,2,3,3-Hexafluoropropane 50 75 82 12 35 Butane, 2,2-dimethyl- 51 26 28 81 69 .1,2,3-Trifluorocyclopentane 52 35 56 52 62 Tetramethyl silane 53 63 33 102 8 1,1,2,2-Tetrafluorocyclobutane 54 44 59 45 59 1,1,2,3,4,4-Hexafluoro-l-butene 55 14 88 34 72 2-Propanone, 1,1,1,3,3-pentafluoro- 56 96 77 15 22 Propane, 1,1,I-trifluoro- 57 51 42 31 86 Trifluoromethyl ethyl ether 58 39 52 63 56 1,3-Difluoroacetone 59 60 37 48 67 1,1,3,3-Tetrafluorooxetane 60 82 63 58 10 1,2-Difluorocyclopentane 61 27 46 66 74 1-Trifluoromethoxy-2-fluoroethane 62 42 67 55 50 I-Fluoro-2-ethy1cyclopropane 63 34 31 95 54 I-Propene, 1,1,2,3,3,3-hexafluoro- 64 15 81 22 97 I-Methoxy-2,2,2-trifluoroethane 65 48 51 62 55 Fluorocyclopentane 66 23 29 82 82 Bis-2,2,2-trifluoroethyl ether 67 64 99 17 38 Ethane, 1,I-difluoro- 68 76 8 40 94 1,2,3,4-Tetrafluorocyclopentane 69 47 74 53 47

16 r.

Rank Name Overall GWP 

### MW Te BP 1,1,2,3,3-Pentafluoropropane 47 83 68 6 41 1,1,1,3

-Tetrafluoroacetone 48 90 60 36 13 Methyl trifluoroacetate 49 71 57 26 49 I,I,2,2,3,3-Hexafluoropropane 50 75 82 12 35 Butane, 2,2-dimethyl- 51 26 28 81 69 .1,2,3-Trifluorocyclopentane 52 35 56 52 62 Tetramethyl silane 53 63 33 102 8 1,1,2,2-Tetrafluorocyclobutane 54 44 59 45 59 1,1,2,3,4,4-Hexafluoro-l-butene 55 14 88 34 72 2-Propanone, 1,1,1,3,3-pentafluoro- 56 96 77 15 22 Propane, 1,1,I-trifluoro- 57 51 42 31 86 Trifluoromethyl ethyl ether 58 39 52 63 56 1,3-Difluoroacetone 59 60 37 48 67 1,1,3,3-Tetrafluorooxetane 60 82 63 58 10 1,2-Difluorocyclopentane 61 27 46 66 74 1-Trifluoromethoxy-2-fluoroethane 62 42 67 55 50 I-Fluoro-2-ethy1cyclopropane 63 34 31 95 54 I-Propene, 1,1,2,3,3,3-hexafluoro- 64 15 81 22 97 I-Methoxy-2,2,2-trifluoroethane 65 48 51 62 55 Fluorocyclopentane 66 23 29 82 82 Bis-2,2,2-trifluoroethyl ether 67 64 99 17 38 Ethane, 1,I-difluoro- 68 76 8 40 94 1,2,3,4-Tetrafluorocyclopentane 69 47 74 53 47

16Rank Name 

### Overall GWP MW TC BP Methane, difluoro- 70 89 2 29 104 1,1,1,2,2,3-Hexafluoropropane 71 62 83 18 63 t-Butyl methyl ether 72 25 30 94 80 Propane, 2-fluoro-2-methyl- 73 46 23 91 73 1-Trifluoromethyl-1,2,2- trifluorocyclobutane 74 45 98 56 36 1,1,1,2,3,3-Hexafluoropropane 75 88 85 20 46 2-Fluoroethylcyclopropane 76 37 32 96

------------- 75 Ethane, pentafluoroiodo- 77 100 103 7 32 Methane, iodofluoro- 78 79 87 1 77 Ethane, 1,1,1,2-tetrafluoro- 79 92 45 11 96 Ethane, fluoro- 80 52 1 90 101 Ethane, 1-iodo-1,1,2,2-tetrafluoro- 81 97 102 3 43 Propane, 1,1,1,2,2,3,3-heptafluoro-3-iodo82 99 104 4 42 Difluoromethyl ether 83 84 54 64 48 Propane,1,1,1,2,3,3,3-heptafluoro-2-iodo- 84 101 105 8 37 1,1,1,2,2-Pentafluoropropane 85 55 72 41 88 1,1,1,3,3,3-Hexafluoropropane 86 94 84 19 61 Methane, trifluoroiodo- 87 61 101 5 92 1 -Methoxy- 1, 1,2,2-tetrafluoroethane 88 65 64 47 84 1-Difluormethoxy-2,2-difluoroethane 89 85 65 50 64 1-Difluoromethoxy-1,1-difluoroethane 90 69 66 51 85 1,1,2,3,3,3-Pentafluoropropyl methyl ether 91 66 100 30 78

17 Rank Name Overall GWP 

### MW TC BP Methane, difluoro- 70 89 2 29 104 1,1,1,2,2,3

-Hexafluoropropane 71 62 83 18 63 t-Butyl methyl ether 72 25 30 94 80 Propane, 2-fluoro-2-methyl- 73 46 23 91 73 1-Trifluoromethyl-l,2,2- 74 45 98 56 36 trifluorocyclobutane 1, 1,I,2,3,3-Hexafluoropropane 75 88 85 20 46 2-Fluoroethylcyclopropane 76 37 32 96 75 Ethane, pentafluoroiodo- 77 100 103 7 32 Methane, iodofluoro- 78 79 87 1 77 Ethane, 1,1,I,2-tetrafluoro- 79 92 45 11 96 Ethane, fluoro- 80 52 1 90 101 Ethane, l-iodo-l,1;2,2-tetrafluoro- 81 97 102 3 43 Propane, 1,1,1,2,2,3,3-heptafluoro-3- 82 99 104 4 42iodoDifluoromethyl ether, 83 84 54 64 48 Propane, 1,1,1,2,3,3,3-heptafluoro-2-iodo- 84 101 105 8 37 1,1,1,2,2-Pentafluoropropane , 85 55 72 41 88 1, 1, 1,3,3,3-Hexafluoropropane 86 94 84 19 61 Methane, trifluoroiodo- 87 61 101 5 92 I-Methoxy-l, 1,2,2-tetrafluoroethane 88 65 64 47 84 1-Difluormethoxy-2,2-difluoroethane 89 85 65 50 64 I-Difluoromethoxy-l,l-difluoroethane 90 69 66 51 85 1, 1,2,3,3,3-Pentafluoropropyl methyl 91 66 100 30 78 ether

17 Rank Name Overall GWP 

### MW TC BP Methane, difluoro- 70 89 2 29 104 1,1,1,2,2,3

-Hexafluoropropane 71 62 83 18 63 t-Butyl methyl ether 72 25 30 94 80 Propane, 2-fluoro-2-methyl- 73 46 23 91 73 1-Trifluoromethyl-l,2,2- 74 45 98 56 36 trifluorocyclobutane 1, 1,I,2,3,3-Hexafluoropropane 75 88 85 20 46 2-Fluoroethylcyclopropane 76 37 32 96 75 Ethane, pentafluoroiodo- 77 100 103 7 32 Methane, iodofluoro- 78 79 87 1 77 Ethane, 1,1,I,2-tetrafluoro- 79 92 45 11 96 Ethane, fluoro- 80 52 1 90 101 Ethane, l-iodo-l,1;2,2-tetrafluoro- 81 97 102 3 43 Propane, 1,1,1,2,2,3,3-heptafluoro-3- 82 99 104 4 42iodoDifluoromethyl ether, 83 84 54 64 48 Propane, 1,1,1,2,3,3,3-heptafluoro-2-iodo- 84 101 105 8 37 1,1,1,2,2-Pentafluoropropane , 85 55 72 41 88 1, 1, 1,3,3,3-Hexafluoropropane 86 94 84 19 61 Methane, trifluoroiodo- 87 61 101 5 92 I-Methoxy-l, 1,2,2-tetrafluoroethane 88 65 64 47 84 1-Difluormethoxy-2,2-difluoroethane 89 85 65 50 64 I-Difluoromethoxy-l,l-difluoroethane 90 69 66 51 85 1, 1,2,3,3,3-Pentafluoropropyl methyl 91 66 100 30 78 ether

17Rank Name 

### Overall GWP MW TC BP Ethane, pentafluoro- 92 95 55 25 103 1 -Difluoromethoxy- 1, 1,2,2- tetrafluoroethane 93 74 93 42 71
1,1,2,2,3-Pentafluorooxetane 94 78 78 80 53 1-Difluoromethoxy-1,2,2-trifluoroethane 95 80 80 44 87 Trifluoromethyl methyl ether 96 67 44. 87 93 2,3,4,5-Tratrfl ourotetrahydrofu ran 97 57 75 100 66 1,1,1,2,2,3,3-Heptafluoropropane 98 81 95 35 89 1-Propene, 3,3,3-trifluoro-2- (trifluoromethyl)- 99 9 89 105 99 Hexafluorocyclopropane 100 102 79 28 102 1,1,1,2,3,3,3-Heptafluoropropane 101 98 94 33 91 Trifluoromethyl ether 102 103 86 72 105 Trifluoromethyl difluoromethyl ether 103 91 73 . 104 100 1,1,2,2,3,3-Hexafluorooxetane 104 104 90 88 98 2-Propanone, hexafluoro- 105 105 91 89 ::^q5

18

# DRA~T

Rank Name Overall 

### GWP MW TC BP Ethane, pentafluoro- 92 95 55 25 103 1-Difluoromethoxy-1, 1,2,2- 93 74 93 42 71 tetrafluoroethane 1,I,2,2,3-Pentafluorooxetane 94 78 78 80 53 I-Difluoromethoxy-I,2,2-trifluoroethane 95 80 80 44 87 Trifluoromethyl methyl ether 96 67 44. 87 93 2,3,4,5-Tratrflourotetrahydrofuran 97 57 75 100 66 1, 1,I,2,2,3,3-Heptafluoropropane 98 81 95 35 89 I-Propene,3,3,3-trifluoro-2- 99 9 89 105 99 (trifluoromethyl)- Hexafluorocyclopropane 100 102 79 28 102 1,1,1,2,3,3,3-Heptafluoropropane 101 98 94 33 91 Trifluoromethyl ether 102 103 86 72 105 Trifluoromethyl difluoromethyl ether 103 91 73 104 100 1, 1,2,2,3,3

-Hexafluorooxetane 104 104 90 88 98 2-Propanone, hexafluoro- 105 105 91 89 95

18

# DRA~T

Rank Name Overall 

### GWP MW TC BP Ethane, pentafluoro- 92 95 55 25 103 1-Difluoromethoxy-1, 1,2,2- 93 74 93 42 71 tetrafluoroethane 1,I,2,2,3-Pentafluorooxetane 94 78 78 80 53 I-Difluoromethoxy-I,2,2-trifluoroethane 95 80 80 44 87 Trifluoromethyl methyl ether 96 67 44. 87 93 2,3,4,5-Tratrflourotetrahydrofuran 97 57 75 100 66 1, 1,I,2,2,3,3-Heptafluoropropane 98 81 95 35 89 I-Propene,3,3,3-trifluoro-2- 99 9 89 105 99 (trifluoromethyl)- Hexafluorocyclopropane 100 102 79 28 102 1,1,1,2,3,3,3-Heptafluoropropane 101 98 94 33 91 Trifluoromethyl ether 102 103 86 72 105 Trifluoromethyl difluoromethyl ether 103 91 73 104 100 1, 1,2,2,3,3

-Hexafluorooxetane 104 104 90 88 98 2-Propanone, hexafluoro- 105 105 91 89 95

18